Rhenium(V)-Imido complexes with potentially multidentate ligands containing the amino group
- Authors: Booysen, Irvin Noel
- Date: 2007
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10385 , http://hdl.handle.net/10948/479 , Rhenium , Ligands
- Description: The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab=1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. The complex trans-[Re(ada)Cl3(PPh3)2] (H2ada=2-aminodiphenylamine) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2ada in acetonitrile. The ligand ada is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. Surprisingly, the Re-Cl bond length trans to the Re=N bond is shorter than the two equatorial Re-Cl bond lengths. The reaction of equimolar quantities of cis-[ReO2I(PPh3)2] with 5,6-diamino-1,3- dimethyluracil (H2ddd) in acetonitrile led to the formation of [Re(ddd)(Hddd)I(PPh3)2](ReO4). The X-ray crystal structure shows that the ligand ddd is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hddd is coordinated bidentately via the neutral amino nitrogen, which is coordinated trans to the imido nitrogen, and the singly deprotonated amido nitrogen, trans to the iodide. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux conditions led to the isolation of [C12H12N6O4] as only product. The [ReO4]- ion is therefore instrumental in the formation of [C12H12N6O4], and since the product contains no rhenium in any oxidation state, the conclusion is that [ReO4]- catalyses the oxidative deamination of H2ddd. The X-ray crystal structure consists of two centrosymmetric, tricyclic rings, comprising a central pyrazine ring and two terminal pyrimidine rings. The reaction of a twofold molar excess of H2apb (H2apb=2-(2-aminophenyl)-1Hbenzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of the formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonal-bipyramidal environment. The two imidazole N(2) atoms lie in the apical positions trans to each other, with the oxo-oxygen and two amido N(1) atoms in the trigonal plane. The complex has C2-symmetry. The two amino groups are singly deprotonated and provide a negative charge each, so that they are coordinated as amides. The oxo group provides two negative charges. In order to obtain electroneutrality for the rhenium(V) complex, the two coordinated imidazole nitrogens provide one negative charge. The complex salt trans-[Re(mps)Cl(PPh3)2](ReO4) (H3mps=N-(2-amino-3- methylphenyl)salicylideneimine) was prepared by the reaction of trans- [ReOCl3(PPh3)2] with a twofold molar excess of H3mps. The X-ray crystal structure shows that the trianionic ligand mps acts as a tridentate chelate via the doubly deprotonated amino nitrogen (which is present in trans- [Re(mps)Cl(PPh3)2](ReO4) as an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. The [ReO4]- anion has approximately regular tetrahedral geometry. Two significant hydrogen bonds are formed between two of the perrhenyl oxygens and the water of crystallization. The six-coordinated complex cis-[Re(mps)Cl2(PPh3)2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps in benzene. The Xray crystal structure shows that the mps ligand coordinates as a tridentate chelate via the doubly deprotonated 2-amino nitrogen, the neutral imino nitrogen and the phenolate oxygen. The imide and phenolate oxygen coordinate trans to each other in a distorted octahedral geometry around the rhenium(V) centre, with the two chlorides in cis positions.
- Full Text:
- Date Issued: 2007
- Authors: Booysen, Irvin Noel
- Date: 2007
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10385 , http://hdl.handle.net/10948/479 , Rhenium , Ligands
- Description: The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab=1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. The complex trans-[Re(ada)Cl3(PPh3)2] (H2ada=2-aminodiphenylamine) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2ada in acetonitrile. The ligand ada is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. Surprisingly, the Re-Cl bond length trans to the Re=N bond is shorter than the two equatorial Re-Cl bond lengths. The reaction of equimolar quantities of cis-[ReO2I(PPh3)2] with 5,6-diamino-1,3- dimethyluracil (H2ddd) in acetonitrile led to the formation of [Re(ddd)(Hddd)I(PPh3)2](ReO4). The X-ray crystal structure shows that the ligand ddd is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hddd is coordinated bidentately via the neutral amino nitrogen, which is coordinated trans to the imido nitrogen, and the singly deprotonated amido nitrogen, trans to the iodide. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux conditions led to the isolation of [C12H12N6O4] as only product. The [ReO4]- ion is therefore instrumental in the formation of [C12H12N6O4], and since the product contains no rhenium in any oxidation state, the conclusion is that [ReO4]- catalyses the oxidative deamination of H2ddd. The X-ray crystal structure consists of two centrosymmetric, tricyclic rings, comprising a central pyrazine ring and two terminal pyrimidine rings. The reaction of a twofold molar excess of H2apb (H2apb=2-(2-aminophenyl)-1Hbenzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of the formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonal-bipyramidal environment. The two imidazole N(2) atoms lie in the apical positions trans to each other, with the oxo-oxygen and two amido N(1) atoms in the trigonal plane. The complex has C2-symmetry. The two amino groups are singly deprotonated and provide a negative charge each, so that they are coordinated as amides. The oxo group provides two negative charges. In order to obtain electroneutrality for the rhenium(V) complex, the two coordinated imidazole nitrogens provide one negative charge. The complex salt trans-[Re(mps)Cl(PPh3)2](ReO4) (H3mps=N-(2-amino-3- methylphenyl)salicylideneimine) was prepared by the reaction of trans- [ReOCl3(PPh3)2] with a twofold molar excess of H3mps. The X-ray crystal structure shows that the trianionic ligand mps acts as a tridentate chelate via the doubly deprotonated amino nitrogen (which is present in trans- [Re(mps)Cl(PPh3)2](ReO4) as an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. The [ReO4]- anion has approximately regular tetrahedral geometry. Two significant hydrogen bonds are formed between two of the perrhenyl oxygens and the water of crystallization. The six-coordinated complex cis-[Re(mps)Cl2(PPh3)2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps in benzene. The Xray crystal structure shows that the mps ligand coordinates as a tridentate chelate via the doubly deprotonated 2-amino nitrogen, the neutral imino nitrogen and the phenolate oxygen. The imide and phenolate oxygen coordinate trans to each other in a distorted octahedral geometry around the rhenium(V) centre, with the two chlorides in cis positions.
- Full Text:
- Date Issued: 2007
Rhenium (I) and (V) complexes with potentially mulidentate ligands containing the Amino group
- Authors: Booysen, Irvin Noel
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10386 , http://hdl.handle.net/10948/1270 , Rhenium , Ligands
- Description: The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab = 1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only in a distorted octahedral coordination geometry around the metal ion. The complex trans- [Re(ada)Cl3(PPh3)2] (H2ada = 2-aminodiphenylamine) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2ada in acetonitrile. The ligand ada is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. The ‘2 + 1’ complex fac- [Re(CO)3(Hamp)(amp)] (Hamp = 2-aminophenol) was isolated from the reaction of a two molar ratio of Hamp with [Re(CO)5Br] in toluene. The reaction of a 1:1 molar ratio of [Re(CO)5Br] and H2ada led to the isolation of the Re(I) complex, fac- [Re(CO)3Br(H2ada)]. The reaction of equimolar quantities of cis-[ReO2I(PPh3)2] with 5,6-diamino-1,3- dimethyluracil (H2ddd) in acetonitrile led to the formation of [Re(ddd)(Hddd)I(PPh3)2](ReO4). The X-ray crystal structure shows that the ligand ddd is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hddd is coordinated bidentately via the neutral amino nitrogen, which is coordinated trans to the imido nitrogen, and the singly deprotonated amido nitrogen, trans to the iodide. The reaction of trans-[ReOCl3(PPh3)2] with N-(2-aminobenzylidene)-5-amino-1,3-dimethyl uracil (H3dua) in ethanol gave a mixed crystal which contains both the neutral oxorhenium(V) complex [ReOCl(Hdua)] and the imido rhenium(V) [Re(dua)Cl2(PPh3)] in an equimolar ratio in the asymmetric unit. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux led to the isolation of [C12H12N6O4] as only product. The [ReO4]- anion is therefore instrumental in the formation of [C12H12N6O4], and since the product contains no rhenium in any oxidation state, the conclusion is that [ReO4]- catalyses the oxidative deamination Abstract I.N. Booysen Nelson Mandela Metropolitan University vii of H2ddd. The X-ray crystal structure consists of two centrosymmetric, tricyclic rings, comprising a central pyrazine ring and two terminal pyrimidine rings. The reaction of 2-(2-aminophenyl)benzothiazole (Habt) with [Re(CO)5Br] led to the isolation of the rhenium(I) complex fac-[Re(Habt)(CO)3Br]. With trans-[ReOCl3(PPh3)2], the ligand Habt decomposed to form the oxofree rhenium(V) complex [Re(itp)2Cl(PPh3)] (itp = 2-amidophenylthiolate). From the reaction of trans-[ReOBr3(PPh3)2] with 2-(2- hydroxyphenyl)benzothiazole (Hhpd) the complex [ReVOBr2(hpd)(PPh3)] was obtained. The reaction of a twofold molar excess of H2apb (2-(2-aminophenyl)-1-benzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonalbipyramidal environment. The two imidazole N(2) atoms lie in the apical positions trans to each other, with the oxo-oxygen and two amido N(1) atoms in the trigonal plane. A new nitrosylrhenium(II) complex salt, [Re(NO)BrL2(PPh3)2](ReO4) (H2L2 = 2-amino-5- (triphenylphosphino)phenol), is the first example of a complex containing the triphenylphosphonium-amidophenolate ligand L2, formed by the nucleophilic attack of a PPh3 on a coordinated amidophenolate ring. The complex salt trans-[Re(mps)Cl(PPh3)2](ReO4) (H3mps = N-(2-amino-3- methylphenyl)salicylideneimine) was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps. The X-ray crystal structure shows that the trianionic ligand mps acts as a tridentate chelate via the doubly deprotonated amino nitrogen (an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. The six-coordinated complex cis-[Re(mps)Cl2(PPh3)2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps in benzene. The X-ray crystal structure show that the mps ligand coordinates as a tridentate chelate via the doubly deprotonated 2-amino nitrogen, the neutral imino nitrogen and the phenolate oxygen. The imide and phenolate oxygen coordinate trans to each other in a distorted octahedral geometry, around the rhenium(V) centre, with the two chlorides in cis positions. A new oxofree rhenium(V) complex salt, [Re(bbd)2](ReO4) ( H2bbd = N-(2- Abstract I.N. Booysen Nelson Mandela Metropolitan University viii aminobenzylidene)benzene-1,2-diamine), has been synthesized and the chelates bbd are coordinated as dianionic tridentate N,N,N-donor diamidoimines. The rhenium(V) ion is centered in a distorted trigonal prism. The rhenium(I) compound fac-[Re(CO)3(daa)].Hpab.H2O (Hpab = N1,N2-(1,2- phenylene)bis(2-aminobenzamide); Hdaa = 2-amino-N-(2-aminophenyl)benzamide) was synthesized from the reaction of [Re(CO)5Br] with a two equivalents of Hpab in toluene. The monoanionic tridentate ligand daa was formed by the rhenium-mediated cleavage of an amido N-C bond of the potentially tetradentate ligand Hpab. Daa is coordinated as a diaminoamide via three nitrogen-donor atoms. The reaction of a twofold molar excess of H2amben (H2amben = N1,N2-bis(2-aminobenzylidene)ethane-1,2-diamine) with trans- [ReOBr3(PPh3)2] gave the oxorhenium(V) cationic complex [ReO(amben)]X (X = Br-, PF6 -). The Re(V) oxo-bridged compound, {μ-O}[ReO(omben)]2.H2O (H2omben = N1,N2- bis(2-hydroxybenzylidene)ethane-1,2-diamine) was isolated from the reaction of a 2:1 molar ratio of H2omben and trans-[ReO2(py)4]Cl in methanol. The seven-coordinate rhenium(III) complex cation [ReIII(dhp)(PPh3)2]+ was isolated as the [ReO4]- salt from the reaction of cis-[ReVO2I(PPh3)2] with 2,6-bis(2- hydroxyphenyliminomethyl)pyridine (H2dhp) in ethanol. In the complex fac- [Re(CO)3(H2dhp)Br], prepared from [Re(CO)5Br] and H2dhp in toluene, the H2dhp ligand acts as a neutral bidentate N,N-donor chelate. An equimolar ratio reaction of 2-aminobenzaldehyde and 2-(2-aminophenyl)-1- benzimidazole in methanol led to 2-(5,6-dihydrobenzimidazolo[1,2-c]-quinazolin-6- yl)aniline. In an attempt to explore the template formation of this class of ligand with rhenium, the reaction of salicylaldehyde and 2-(2-aminophenyl)-1-benzimidazole in ethanol which was followed by the addition of trans-[ReOBr3(PPh3)2] led to the formation of the salt, 6-(2-hydroxyphenyl)-5,6-dihydrobenzimidazolo[1,2-c]quinazolin- 12-ium bromide. The compound 6-(2-methylthiophenyl)-5,6-dihydrobenzimidazolo[1,2- c]quinazolin-12-ium was synthesized via the reaction of 2-aminobenzaldehyde and 2- methylthiobenzaldehyde in methanol.
- Full Text:
- Date Issued: 2009
- Authors: Booysen, Irvin Noel
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10386 , http://hdl.handle.net/10948/1270 , Rhenium , Ligands
- Description: The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab = 1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only in a distorted octahedral coordination geometry around the metal ion. The complex trans- [Re(ada)Cl3(PPh3)2] (H2ada = 2-aminodiphenylamine) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2ada in acetonitrile. The ligand ada is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. The ‘2 + 1’ complex fac- [Re(CO)3(Hamp)(amp)] (Hamp = 2-aminophenol) was isolated from the reaction of a two molar ratio of Hamp with [Re(CO)5Br] in toluene. The reaction of a 1:1 molar ratio of [Re(CO)5Br] and H2ada led to the isolation of the Re(I) complex, fac- [Re(CO)3Br(H2ada)]. The reaction of equimolar quantities of cis-[ReO2I(PPh3)2] with 5,6-diamino-1,3- dimethyluracil (H2ddd) in acetonitrile led to the formation of [Re(ddd)(Hddd)I(PPh3)2](ReO4). The X-ray crystal structure shows that the ligand ddd is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hddd is coordinated bidentately via the neutral amino nitrogen, which is coordinated trans to the imido nitrogen, and the singly deprotonated amido nitrogen, trans to the iodide. The reaction of trans-[ReOCl3(PPh3)2] with N-(2-aminobenzylidene)-5-amino-1,3-dimethyl uracil (H3dua) in ethanol gave a mixed crystal which contains both the neutral oxorhenium(V) complex [ReOCl(Hdua)] and the imido rhenium(V) [Re(dua)Cl2(PPh3)] in an equimolar ratio in the asymmetric unit. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux led to the isolation of [C12H12N6O4] as only product. The [ReO4]- anion is therefore instrumental in the formation of [C12H12N6O4], and since the product contains no rhenium in any oxidation state, the conclusion is that [ReO4]- catalyses the oxidative deamination Abstract I.N. Booysen Nelson Mandela Metropolitan University vii of H2ddd. The X-ray crystal structure consists of two centrosymmetric, tricyclic rings, comprising a central pyrazine ring and two terminal pyrimidine rings. The reaction of 2-(2-aminophenyl)benzothiazole (Habt) with [Re(CO)5Br] led to the isolation of the rhenium(I) complex fac-[Re(Habt)(CO)3Br]. With trans-[ReOCl3(PPh3)2], the ligand Habt decomposed to form the oxofree rhenium(V) complex [Re(itp)2Cl(PPh3)] (itp = 2-amidophenylthiolate). From the reaction of trans-[ReOBr3(PPh3)2] with 2-(2- hydroxyphenyl)benzothiazole (Hhpd) the complex [ReVOBr2(hpd)(PPh3)] was obtained. The reaction of a twofold molar excess of H2apb (2-(2-aminophenyl)-1-benzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonalbipyramidal environment. The two imidazole N(2) atoms lie in the apical positions trans to each other, with the oxo-oxygen and two amido N(1) atoms in the trigonal plane. A new nitrosylrhenium(II) complex salt, [Re(NO)BrL2(PPh3)2](ReO4) (H2L2 = 2-amino-5- (triphenylphosphino)phenol), is the first example of a complex containing the triphenylphosphonium-amidophenolate ligand L2, formed by the nucleophilic attack of a PPh3 on a coordinated amidophenolate ring. The complex salt trans-[Re(mps)Cl(PPh3)2](ReO4) (H3mps = N-(2-amino-3- methylphenyl)salicylideneimine) was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps. The X-ray crystal structure shows that the trianionic ligand mps acts as a tridentate chelate via the doubly deprotonated amino nitrogen (an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. The six-coordinated complex cis-[Re(mps)Cl2(PPh3)2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps in benzene. The X-ray crystal structure show that the mps ligand coordinates as a tridentate chelate via the doubly deprotonated 2-amino nitrogen, the neutral imino nitrogen and the phenolate oxygen. The imide and phenolate oxygen coordinate trans to each other in a distorted octahedral geometry, around the rhenium(V) centre, with the two chlorides in cis positions. A new oxofree rhenium(V) complex salt, [Re(bbd)2](ReO4) ( H2bbd = N-(2- Abstract I.N. Booysen Nelson Mandela Metropolitan University viii aminobenzylidene)benzene-1,2-diamine), has been synthesized and the chelates bbd are coordinated as dianionic tridentate N,N,N-donor diamidoimines. The rhenium(V) ion is centered in a distorted trigonal prism. The rhenium(I) compound fac-[Re(CO)3(daa)].Hpab.H2O (Hpab = N1,N2-(1,2- phenylene)bis(2-aminobenzamide); Hdaa = 2-amino-N-(2-aminophenyl)benzamide) was synthesized from the reaction of [Re(CO)5Br] with a two equivalents of Hpab in toluene. The monoanionic tridentate ligand daa was formed by the rhenium-mediated cleavage of an amido N-C bond of the potentially tetradentate ligand Hpab. Daa is coordinated as a diaminoamide via three nitrogen-donor atoms. The reaction of a twofold molar excess of H2amben (H2amben = N1,N2-bis(2-aminobenzylidene)ethane-1,2-diamine) with trans- [ReOBr3(PPh3)2] gave the oxorhenium(V) cationic complex [ReO(amben)]X (X = Br-, PF6 -). The Re(V) oxo-bridged compound, {μ-O}[ReO(omben)]2.H2O (H2omben = N1,N2- bis(2-hydroxybenzylidene)ethane-1,2-diamine) was isolated from the reaction of a 2:1 molar ratio of H2omben and trans-[ReO2(py)4]Cl in methanol. The seven-coordinate rhenium(III) complex cation [ReIII(dhp)(PPh3)2]+ was isolated as the [ReO4]- salt from the reaction of cis-[ReVO2I(PPh3)2] with 2,6-bis(2- hydroxyphenyliminomethyl)pyridine (H2dhp) in ethanol. In the complex fac- [Re(CO)3(H2dhp)Br], prepared from [Re(CO)5Br] and H2dhp in toluene, the H2dhp ligand acts as a neutral bidentate N,N-donor chelate. An equimolar ratio reaction of 2-aminobenzaldehyde and 2-(2-aminophenyl)-1- benzimidazole in methanol led to 2-(5,6-dihydrobenzimidazolo[1,2-c]-quinazolin-6- yl)aniline. In an attempt to explore the template formation of this class of ligand with rhenium, the reaction of salicylaldehyde and 2-(2-aminophenyl)-1-benzimidazole in ethanol which was followed by the addition of trans-[ReOBr3(PPh3)2] led to the formation of the salt, 6-(2-hydroxyphenyl)-5,6-dihydrobenzimidazolo[1,2-c]quinazolin- 12-ium bromide. The compound 6-(2-methylthiophenyl)-5,6-dihydrobenzimidazolo[1,2- c]quinazolin-12-ium was synthesized via the reaction of 2-aminobenzaldehyde and 2- methylthiobenzaldehyde in methanol.
- Full Text:
- Date Issued: 2009
Rhenium complexes with multidentate benzazoles and related N,X-donor (X = N, O, S) ligands
- Authors: Potgieter, Kim Carey
- Date: 2012
- Subjects: Rhenium , Benzimidazoles , Ligands (Biochemistry)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10438 , http://hdl.handle.net/10948/d1020773
- Description: The coordination behaviour of 4-aminoantipyrine (H2pap) and its Schiff base derivatives with the oxorhenium(V) and tricarbonyl rhenium(I) cores are reported. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with H2pap were studied, and the complexes cis-[ReX2(pap)(H2pap)(PPh3)](ReO4) were isolated. The ligand pap is coordinated monodentately through the doubly deprotonated amino nitrogen as an imide, and H2pap acts as a neutral bidentate chelate, with coordination through the neutral amino nitrogen and the ketonic oxygen. The reactions of trans-[ReOBr3(PPh3)2] and cis-[ReO2I(PPh3)2] with -(2-aminobenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (H2nap) and 4-(2-hydroxybenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (Hoap) are also reported. The complexes cis-[Re(nap)Br2(PPh3)]Br, [ReO(OEt)(Hnap)(PPh3)]I and [ReO(OMe)(oap)(PPh3)]I were isolated and structurally characterized. The reactions of the Schiff base derivatives 1,2-(diimino-4’-antipyrinyl)ethane (dae) and 2,6-bis(4-amino-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one)pyridine (bap) with [Re(CO)5X] (X = Br or Cl) produced fac-[Re(CO)3(dae)Cl] and fac-[Re(CO)3(bap)Br] respectively. A series of rhenium(I) tricarbonyl complexes containing bidentate derivatives of aniline was synthesized and structurally characterized. With 1,2-diaminobenzene (Hpda) the ‘2+1’ complex salt fac-[Re(CO)3(κ1-Hpda)(κ2-Hpda)]Br was isolated, but with 2-mercaptophenol (Hspo) the bridged dimer [Re2(CO)7(spo)2] was found. The neutral complex [Re(CO)3(ons)(Hno)] was isolated from the reaction of [Re(CO)5Br] with 2-[(2-methylthio)benzylideneimino]phenol (Hons; Hno = 2-aminophenol), with ons coordinated as a bidentate chelate with a free SCH3 group. In the complex [Re(CO)3(Htpn)Br] (Htpn = N-(2-(methylthio)benzylidene)benzene-1,2-diamine) the potentially tridentate ligand Htpn is coordinated via the methylthiol sulfur and imino nitrogen atoms only, with a free amino group. These rhenium(I) complexes, with the exception of [Re2(CO)7(spo)2], revealed broad emissions centred around 535 nm. The reactions of the rhenium(V) complex cis-[ReO2I(PPh3)2] with 2-aminothiophenol (H2atp), benzene-1,2-dithiol (H2tdt) and 2-hydroxybenzenethiol (H2otp) led to the formation of the rhenium(III) compounds [Re(Hatp)(ibsq)2].OPPh3, [Re(sbsq)3].OPPh3 and [Re(obsq)3].OPPh3 (ibsq = 2-iminothiobenzosemiquinonate, sbsq = 1,2-dithiobenzosemiquinonate, obsq = 2-hydroxothiobenzosemiquinonate) respectively. The complexes adopt a trigonal prismatic geometry around the rhenium centre with average twists angles between 3.20-26.10˚. The E1/2 values for the Re(III)/Re(IV) redox couple were found to be 0.022, 0.142 and 0.126 V for [Re(Hatp)(ibsq)2].OPPh3, [Re(sbsq)3].OPPh3 and [Re(obsq)3].OPPh3 respectively. The reactions of the benzoxazole ligands, 3-(benzoxazol-2-yl)pyridin-2-ol (Hbop) and 5-amino-2-(benzoxazol-2-yl)phenol (Habo) with a [ReO]3+ precursor led to the rhenium(III) complex, [ReCl2(bop)(PPh3)2], and the complex salt, [ReO(abo)I(PPh3)2]ReO4, respectively. A variety of benzothiazole and benzimidazole derivatives were reacted with [Re(CO)5Br]. In the case of bis(benzothiazol-2-ylethyl)sulfide (bts), the neutral complex fac-[Re(CO)3(bts)Br] was obtained. The dimeric complexes (μ-dbt)2[Re(CO)3]2 and (μ-mbt)2[Re(CO)3]2 were formed when 1,3-bis(benzothiazol-2-yl)thiourea (Hdbt) and 1-(benzothiazol-2-ylidene)-3-methylthiourea (Hmbt) were used as ligands. The reaction of 2,2’-(oxybis(methylene))bis(benzimidazole) (bmb) with [Re(CO)5Cl] resulted in the rhenium(I) complex salt fac-[Re(CO)3(bmb)]+, with the tri-μ-chlorohexacarbonyl dirhenate [Re2(CO)6Cl3]- as the counter anion. The neutral complex fac-[Re(CO)3(btp)Cl] was isolated from the reaction of the 2,9-bis(benzothiazol-2-yl)-1,10-phenanthroline (btp) ligand and [Re(CO)5Cl]. The reactions of trans-[ReOCl3(PPh3)2] with bis(benzimidazol-2-ylethyl)sulfide (btn) and 1-(benzothiazol-2-ylidene)-3-methylthiourea (Hmbt) led to the formation of the cationic compounds (μ-O)2[Re2O2(btn)2]I2 and [ReCl2(bte)(PPh3)2]Cl (bte = (benzothiazole-2-yl)-N-ethylidenemethanamine) respectively.
- Full Text:
- Date Issued: 2012
- Authors: Potgieter, Kim Carey
- Date: 2012
- Subjects: Rhenium , Benzimidazoles , Ligands (Biochemistry)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10438 , http://hdl.handle.net/10948/d1020773
- Description: The coordination behaviour of 4-aminoantipyrine (H2pap) and its Schiff base derivatives with the oxorhenium(V) and tricarbonyl rhenium(I) cores are reported. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with H2pap were studied, and the complexes cis-[ReX2(pap)(H2pap)(PPh3)](ReO4) were isolated. The ligand pap is coordinated monodentately through the doubly deprotonated amino nitrogen as an imide, and H2pap acts as a neutral bidentate chelate, with coordination through the neutral amino nitrogen and the ketonic oxygen. The reactions of trans-[ReOBr3(PPh3)2] and cis-[ReO2I(PPh3)2] with -(2-aminobenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (H2nap) and 4-(2-hydroxybenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (Hoap) are also reported. The complexes cis-[Re(nap)Br2(PPh3)]Br, [ReO(OEt)(Hnap)(PPh3)]I and [ReO(OMe)(oap)(PPh3)]I were isolated and structurally characterized. The reactions of the Schiff base derivatives 1,2-(diimino-4’-antipyrinyl)ethane (dae) and 2,6-bis(4-amino-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one)pyridine (bap) with [Re(CO)5X] (X = Br or Cl) produced fac-[Re(CO)3(dae)Cl] and fac-[Re(CO)3(bap)Br] respectively. A series of rhenium(I) tricarbonyl complexes containing bidentate derivatives of aniline was synthesized and structurally characterized. With 1,2-diaminobenzene (Hpda) the ‘2+1’ complex salt fac-[Re(CO)3(κ1-Hpda)(κ2-Hpda)]Br was isolated, but with 2-mercaptophenol (Hspo) the bridged dimer [Re2(CO)7(spo)2] was found. The neutral complex [Re(CO)3(ons)(Hno)] was isolated from the reaction of [Re(CO)5Br] with 2-[(2-methylthio)benzylideneimino]phenol (Hons; Hno = 2-aminophenol), with ons coordinated as a bidentate chelate with a free SCH3 group. In the complex [Re(CO)3(Htpn)Br] (Htpn = N-(2-(methylthio)benzylidene)benzene-1,2-diamine) the potentially tridentate ligand Htpn is coordinated via the methylthiol sulfur and imino nitrogen atoms only, with a free amino group. These rhenium(I) complexes, with the exception of [Re2(CO)7(spo)2], revealed broad emissions centred around 535 nm. The reactions of the rhenium(V) complex cis-[ReO2I(PPh3)2] with 2-aminothiophenol (H2atp), benzene-1,2-dithiol (H2tdt) and 2-hydroxybenzenethiol (H2otp) led to the formation of the rhenium(III) compounds [Re(Hatp)(ibsq)2].OPPh3, [Re(sbsq)3].OPPh3 and [Re(obsq)3].OPPh3 (ibsq = 2-iminothiobenzosemiquinonate, sbsq = 1,2-dithiobenzosemiquinonate, obsq = 2-hydroxothiobenzosemiquinonate) respectively. The complexes adopt a trigonal prismatic geometry around the rhenium centre with average twists angles between 3.20-26.10˚. The E1/2 values for the Re(III)/Re(IV) redox couple were found to be 0.022, 0.142 and 0.126 V for [Re(Hatp)(ibsq)2].OPPh3, [Re(sbsq)3].OPPh3 and [Re(obsq)3].OPPh3 respectively. The reactions of the benzoxazole ligands, 3-(benzoxazol-2-yl)pyridin-2-ol (Hbop) and 5-amino-2-(benzoxazol-2-yl)phenol (Habo) with a [ReO]3+ precursor led to the rhenium(III) complex, [ReCl2(bop)(PPh3)2], and the complex salt, [ReO(abo)I(PPh3)2]ReO4, respectively. A variety of benzothiazole and benzimidazole derivatives were reacted with [Re(CO)5Br]. In the case of bis(benzothiazol-2-ylethyl)sulfide (bts), the neutral complex fac-[Re(CO)3(bts)Br] was obtained. The dimeric complexes (μ-dbt)2[Re(CO)3]2 and (μ-mbt)2[Re(CO)3]2 were formed when 1,3-bis(benzothiazol-2-yl)thiourea (Hdbt) and 1-(benzothiazol-2-ylidene)-3-methylthiourea (Hmbt) were used as ligands. The reaction of 2,2’-(oxybis(methylene))bis(benzimidazole) (bmb) with [Re(CO)5Cl] resulted in the rhenium(I) complex salt fac-[Re(CO)3(bmb)]+, with the tri-μ-chlorohexacarbonyl dirhenate [Re2(CO)6Cl3]- as the counter anion. The neutral complex fac-[Re(CO)3(btp)Cl] was isolated from the reaction of the 2,9-bis(benzothiazol-2-yl)-1,10-phenanthroline (btp) ligand and [Re(CO)5Cl]. The reactions of trans-[ReOCl3(PPh3)2] with bis(benzimidazol-2-ylethyl)sulfide (btn) and 1-(benzothiazol-2-ylidene)-3-methylthiourea (Hmbt) led to the formation of the cationic compounds (μ-O)2[Re2O2(btn)2]I2 and [ReCl2(bte)(PPh3)2]Cl (bte = (benzothiazole-2-yl)-N-ethylidenemethanamine) respectively.
- Full Text:
- Date Issued: 2012
Fishing rights, redistribution and policy : the South African commercial T.A.C. fisheries
- Authors: Mather, Diarmid John
- Date: 2005
- Subjects: Fisheries -- South Africa Fish trade -- South Africa Fishery law and legislation -- South Africa Fishery policy -- South Africa Fishery management -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1061 , http://hdl.handle.net/10962/d1007531
- Description: The main objective of this thesis is to provide an analysis of the economic logic behind fisheries policy and redistribution in South African. An examination of the institutional and organizational evolution reveals that South African fisheries policy followed the world trend in the movement toward quota management systems. However, it is argued that due to the peculiarities of the Apartheid political system, South Africa developed a unique and persistent structure of individual fishing rights that resulted in a transfer of power from the fisher to monopsonistic, and subsequently vertically integrated, fish processing companies. Problems, however, arose with the need to redistribute fishing rights to previously repressed racial groups. It is proposed that, within a specific form (TAC), the structure of individual fishing rights can be decomposed into four operational rules, namely, the right of participation, asset size, tradability and duration of term. Policy design is restricted to a feasible set of rules that impact on the flexibility of the system, the incentives facing private fishing companies and fishers, the efficiency of the fisheries management plan and finally the effect it has on a redistribution strategy. Within this analytical framework, South Africa's policy yields a very flexible system favourable to monopsonistic industrial organisation. However, by adding a redistribution constraint, this structure has a number of important effects. First, as new quota holders are added the information costs for effective fisheries management increase exponentially. Second, the transaction costs to private fishing companies are increased. Third, only the resource rent is redistributed (weak redistribution). Next, the micro to small vessel fisheries, the medium vessel fisheries and the large vessel fisheries are examined separately. The major aim is to determine, within the available data, the effect that a weak redistribution policy (redistribution of the resource rent), has on strong redistribution (redistribution of fishing capital and skills). The evidence definitely supports the analytical framework and suggests that fundamentally the structure of individual fishing rights, which evolved in response to a monopsonistic industrial organisation during the apartheid era in South Africa, works against strong redistribution. Also, that different fisheries face different constraints and that these should in certain instances be treated separately.
- Full Text:
- Date Issued: 2005
- Authors: Mather, Diarmid John
- Date: 2005
- Subjects: Fisheries -- South Africa Fish trade -- South Africa Fishery law and legislation -- South Africa Fishery policy -- South Africa Fishery management -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1061 , http://hdl.handle.net/10962/d1007531
- Description: The main objective of this thesis is to provide an analysis of the economic logic behind fisheries policy and redistribution in South African. An examination of the institutional and organizational evolution reveals that South African fisheries policy followed the world trend in the movement toward quota management systems. However, it is argued that due to the peculiarities of the Apartheid political system, South Africa developed a unique and persistent structure of individual fishing rights that resulted in a transfer of power from the fisher to monopsonistic, and subsequently vertically integrated, fish processing companies. Problems, however, arose with the need to redistribute fishing rights to previously repressed racial groups. It is proposed that, within a specific form (TAC), the structure of individual fishing rights can be decomposed into four operational rules, namely, the right of participation, asset size, tradability and duration of term. Policy design is restricted to a feasible set of rules that impact on the flexibility of the system, the incentives facing private fishing companies and fishers, the efficiency of the fisheries management plan and finally the effect it has on a redistribution strategy. Within this analytical framework, South Africa's policy yields a very flexible system favourable to monopsonistic industrial organisation. However, by adding a redistribution constraint, this structure has a number of important effects. First, as new quota holders are added the information costs for effective fisheries management increase exponentially. Second, the transaction costs to private fishing companies are increased. Third, only the resource rent is redistributed (weak redistribution). Next, the micro to small vessel fisheries, the medium vessel fisheries and the large vessel fisheries are examined separately. The major aim is to determine, within the available data, the effect that a weak redistribution policy (redistribution of the resource rent), has on strong redistribution (redistribution of fishing capital and skills). The evidence definitely supports the analytical framework and suggests that fundamentally the structure of individual fishing rights, which evolved in response to a monopsonistic industrial organisation during the apartheid era in South Africa, works against strong redistribution. Also, that different fisheries face different constraints and that these should in certain instances be treated separately.
- Full Text:
- Date Issued: 2005
Novel aspects of platinum-amine coordination compounds: their chemistry and anticancer application
- Authors: Bouwer, Yolanda
- Date: 2008
- Subjects: Coordination compounds , Platinum compounds , Antineoplastic agents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10444 , http://hdl.handle.net/10948/d1021052
- Description: The aim in this thesis, was to synthesize novel platinum coordination compounds, in order to develop compounds with improved anticancer action which could lead to an improved understanding of the mechanism by which they operate and at the same time, improve synthetic methods for their products. The initial work included the development of a novel synthetic method for 1R,2R-diaminocyclohexaneoxalato-platinum(II) (oxaliplatin), by using an essentially non-aqueous solvent medium and direct ligand exchange at elevated temperatures. This was done by a study of the kinetics of the reaction in a variety of conditions; such as relative reagent concentrations and ratios as well as solvent mixtures. An effective method was developed which could be applied industrially. An international patent was taken out on this method. Various amine complexes of platinum(II) were synthesized using chloro, bromo and oxalato groups as leaving groups. The non-leaving groups were selected having certain specific characteristics in mind. Novel mononitroplatinum(IV) complexes were synthesized, mostly with oxalato leaving groups. One of these in particular, had excellent anticancer behaviour. Another trichloromononitro complex was also synthesized with very good anticancer properties. Two international patents were filed for the latter two compounds. As far as possible, all compounds were studied by spectrometric, chromatographic and thermal methods. They were also tested against 3 cancer cell lines namely cervical (Hela), Colon (HT29) and Breast (MCF7) cancer cells.
- Full Text:
- Date Issued: 2008
- Authors: Bouwer, Yolanda
- Date: 2008
- Subjects: Coordination compounds , Platinum compounds , Antineoplastic agents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10444 , http://hdl.handle.net/10948/d1021052
- Description: The aim in this thesis, was to synthesize novel platinum coordination compounds, in order to develop compounds with improved anticancer action which could lead to an improved understanding of the mechanism by which they operate and at the same time, improve synthetic methods for their products. The initial work included the development of a novel synthetic method for 1R,2R-diaminocyclohexaneoxalato-platinum(II) (oxaliplatin), by using an essentially non-aqueous solvent medium and direct ligand exchange at elevated temperatures. This was done by a study of the kinetics of the reaction in a variety of conditions; such as relative reagent concentrations and ratios as well as solvent mixtures. An effective method was developed which could be applied industrially. An international patent was taken out on this method. Various amine complexes of platinum(II) were synthesized using chloro, bromo and oxalato groups as leaving groups. The non-leaving groups were selected having certain specific characteristics in mind. Novel mononitroplatinum(IV) complexes were synthesized, mostly with oxalato leaving groups. One of these in particular, had excellent anticancer behaviour. Another trichloromononitro complex was also synthesized with very good anticancer properties. Two international patents were filed for the latter two compounds. As far as possible, all compounds were studied by spectrometric, chromatographic and thermal methods. They were also tested against 3 cancer cell lines namely cervical (Hela), Colon (HT29) and Breast (MCF7) cancer cells.
- Full Text:
- Date Issued: 2008
Salinity induced physiological responses in juvenile dusky kob, Argyrosomus japonicus (Sciaenidae)
- Authors: Bernatzeder, Andrea Katinka
- Date: 2009
- Subjects: Osmoregulation , Argyrosomus -- Effects of salt on -- South Africa , Sciaenidae -- Effects of salt on -- South Africa , Argyrosomus -- Physiology , Sciaenidae -- Physiology , Fishes -- Physiology , Biological control systems , Marine ecology -- South Africa , Fishery management -- South Africa , Mariculture -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5318 , http://hdl.handle.net/10962/d1005163 , Osmoregulation , Argyrosomus -- Effects of salt on -- South Africa , Sciaenidae -- Effects of salt on -- South Africa , Argyrosomus -- Physiology , Sciaenidae -- Physiology , Fishes -- Physiology , Biological control systems , Marine ecology -- South Africa , Fishery management -- South Africa , Mariculture -- South Africa
- Description: Fisheries management regulations for dusky kob Argyrosomus japonicus, an important commercial and recreational fisheries species, have failed and the stock is considered collapsed. It is important to take an ecosystems approach to management which includes understanding the effect of environmental factors on recruitment, abundance and distribution. The distribution of early juveniles (20-150 mm TL) in the wild appears to be restricted to the upper reaches of estuaries at salinities below 5 psu. Food availability could not explain the distribution of early juveniles. The aim of this study was to investigate the role of salinity on the distribution of early juvenile dusky kob (<150 mm TL) by examining physiological responses of juveniles exposed to a range of salinities under laboratory conditions. The hypothesis was that the physiological functioning of early juveniles would be optimised at the reduced salinities which they naturally occur at. The objectives of this study were to investigate the effect of salinity on: i) plasma osmolality; ii) growth, food conversion ratio and condition factor; and iii) gill histology with emphasis on chloride cell size and number. A preliminary study was undertaken to determine whether the use of 2-phenoxyethanol had an effect on plasma osmolality. Juveniles pithed prior to blood sampling were used as the control. Plasma osmolality was not affected by exposure or duration of exposure (2, 4, 6, 8, 10 min) to 2-phenoxyethanol. The ability of teleosts to regulate plasma osmolality over a wide range of salinities indicates their degree of ‘physiological euryhalinity’. Plasma osmolality of juveniles exposed to 5, 12 and 35 psu was measured every two weeks over a total of six weeks. Although juveniles were able to regulate plasma osmolality over the duration of the experiment, plasma osmolality at 5 and 12 psu was significantly lower than in fish maintained at 35 psu. Growth is used as an indicator of the relative energy used for osmoregulation at different salinities, as the energy used for osmoregulation becomes unavailable for growth. A nineweek growth experiment was conducted on juveniles exposed to 5, 12 and 35 psu. Juveniles grew and survived at all three salinities. However, growth of juveniles at 5 psu was significantly lower than at 12 and 35 psu. Other than a significantly greater weight gain at 35 psu relative to 12 psu, there was no significant difference in specific growth and length gain between juveniles at 12 and 35 psu. Food conversion ratio and condition factor at 12 and 35 psu were not significantly different, but food conversion ratio and condition factor at 5 psu was significantly greater and lower than at 35 psu respectively. In fish, gills are considered the major organ involved in osmoregulation. Within the gills, chloride cells are the predominant site of ion exchange which is driven by the Na⁺, K⁺- ATPase enzyme. Gill samples of juveniles exposed to 5, 12 and 35 psu for six weeks were examined histologically using light microscopy. Chloride cells of juveniles maintained at 5 psu were significantly more abundant than in juveniles at 12 and 35 psu. Chloride cells of juveniles at 5 psu were significantly larger than in juveniles kept at 12 psu, but not significantly different to those of juveniles kept at 35 psu. The ability of the juvenile fish to regulate plasma osmolality indicates that they are 'physiologically euryhaline', but the reduced growth and proliferation of chloride cells at 5 psu suggests that energy expenditure for osmoregulation is increased at hypoosmotic salinities. Salinity induced physiological responses could therefore not explain the natural distribution of early juvenile dusky kob and it is proposed that other environmental factors (e.g. temperature) are also important. It is also hypothesised that the high conductivity of an estuary in South Africa, to which our understanding is limited, may negate the effect of reduced salinity. Although freshwater input into estuaries is an important factor, further investigations to explain the distribution and abundance of early juveniles is required to make management recommendations. Dusky kob is also becoming an increasingly popular aquaculture species in South Africa. In this regard, early juvenile dusky kob can be grown at salinities as low as 12 psu without negatively affecting growth and production.
- Full Text:
- Date Issued: 2009
- Authors: Bernatzeder, Andrea Katinka
- Date: 2009
- Subjects: Osmoregulation , Argyrosomus -- Effects of salt on -- South Africa , Sciaenidae -- Effects of salt on -- South Africa , Argyrosomus -- Physiology , Sciaenidae -- Physiology , Fishes -- Physiology , Biological control systems , Marine ecology -- South Africa , Fishery management -- South Africa , Mariculture -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5318 , http://hdl.handle.net/10962/d1005163 , Osmoregulation , Argyrosomus -- Effects of salt on -- South Africa , Sciaenidae -- Effects of salt on -- South Africa , Argyrosomus -- Physiology , Sciaenidae -- Physiology , Fishes -- Physiology , Biological control systems , Marine ecology -- South Africa , Fishery management -- South Africa , Mariculture -- South Africa
- Description: Fisheries management regulations for dusky kob Argyrosomus japonicus, an important commercial and recreational fisheries species, have failed and the stock is considered collapsed. It is important to take an ecosystems approach to management which includes understanding the effect of environmental factors on recruitment, abundance and distribution. The distribution of early juveniles (20-150 mm TL) in the wild appears to be restricted to the upper reaches of estuaries at salinities below 5 psu. Food availability could not explain the distribution of early juveniles. The aim of this study was to investigate the role of salinity on the distribution of early juvenile dusky kob (<150 mm TL) by examining physiological responses of juveniles exposed to a range of salinities under laboratory conditions. The hypothesis was that the physiological functioning of early juveniles would be optimised at the reduced salinities which they naturally occur at. The objectives of this study were to investigate the effect of salinity on: i) plasma osmolality; ii) growth, food conversion ratio and condition factor; and iii) gill histology with emphasis on chloride cell size and number. A preliminary study was undertaken to determine whether the use of 2-phenoxyethanol had an effect on plasma osmolality. Juveniles pithed prior to blood sampling were used as the control. Plasma osmolality was not affected by exposure or duration of exposure (2, 4, 6, 8, 10 min) to 2-phenoxyethanol. The ability of teleosts to regulate plasma osmolality over a wide range of salinities indicates their degree of ‘physiological euryhalinity’. Plasma osmolality of juveniles exposed to 5, 12 and 35 psu was measured every two weeks over a total of six weeks. Although juveniles were able to regulate plasma osmolality over the duration of the experiment, plasma osmolality at 5 and 12 psu was significantly lower than in fish maintained at 35 psu. Growth is used as an indicator of the relative energy used for osmoregulation at different salinities, as the energy used for osmoregulation becomes unavailable for growth. A nineweek growth experiment was conducted on juveniles exposed to 5, 12 and 35 psu. Juveniles grew and survived at all three salinities. However, growth of juveniles at 5 psu was significantly lower than at 12 and 35 psu. Other than a significantly greater weight gain at 35 psu relative to 12 psu, there was no significant difference in specific growth and length gain between juveniles at 12 and 35 psu. Food conversion ratio and condition factor at 12 and 35 psu were not significantly different, but food conversion ratio and condition factor at 5 psu was significantly greater and lower than at 35 psu respectively. In fish, gills are considered the major organ involved in osmoregulation. Within the gills, chloride cells are the predominant site of ion exchange which is driven by the Na⁺, K⁺- ATPase enzyme. Gill samples of juveniles exposed to 5, 12 and 35 psu for six weeks were examined histologically using light microscopy. Chloride cells of juveniles maintained at 5 psu were significantly more abundant than in juveniles at 12 and 35 psu. Chloride cells of juveniles at 5 psu were significantly larger than in juveniles kept at 12 psu, but not significantly different to those of juveniles kept at 35 psu. The ability of the juvenile fish to regulate plasma osmolality indicates that they are 'physiologically euryhaline', but the reduced growth and proliferation of chloride cells at 5 psu suggests that energy expenditure for osmoregulation is increased at hypoosmotic salinities. Salinity induced physiological responses could therefore not explain the natural distribution of early juvenile dusky kob and it is proposed that other environmental factors (e.g. temperature) are also important. It is also hypothesised that the high conductivity of an estuary in South Africa, to which our understanding is limited, may negate the effect of reduced salinity. Although freshwater input into estuaries is an important factor, further investigations to explain the distribution and abundance of early juveniles is required to make management recommendations. Dusky kob is also becoming an increasingly popular aquaculture species in South Africa. In this regard, early juvenile dusky kob can be grown at salinities as low as 12 psu without negatively affecting growth and production.
- Full Text:
- Date Issued: 2009
Agreement and coordination in XiTsonga, SeSotho and IsiXhosa: an optimality theoretic perspective
- Authors: Mitchley, Hazel
- Date: 2016
- Language: English
- Type: Thesis , Masters , MA
- Identifier: http://hdl.handle.net/10962/3423 , vital:20491
- Description: This thesis provides a unified Optimality Theoretic analysis of subject-verb agreement with coordinated preverbal subjects in three Southern Bantu languages: Xitsonga (S53), Sesotho (S33), and isiXhosa (S41). This analysis is then used to formulate a typology of agreement resolution strategies and the contexts which trigger them. Although some accounts in the Bantu literature suggest that agreement with coordinate structures is avoided by speakers (e.g. Schadeberg 1992, Voeltz 1971) especially when conjuncts are from different noun classes, I show that there is ample evidence to the contrary, and that the subject marker used is dependent on several factors, including (i) the [-HUMAN] specification on the conjuncts, (ii) whether the conjuncts are singular or plural, (iii) whether or not the conjuncts both carry the same noun class feature, and (iv) the order of the conjuncts. This thesis shows that there are various agreement resolution strategies which can beused: 1) agreement with the [+HUMAN] feature on the conjuncts, 2) agreement with the[-HUMAN] feature on the conjuncts, 3) agreement with the noun class feature on both conjuncts, 4) agreement with the noun class feature on the conjunct closest to the verb, and 5) agreement with the noun class feature on the conjunct furthest from the verb. Not all of these strategies are used by all languages, nor are these strategies interchangeable in the languages which do use them – instead, multiple factors conspire to trigger the use of a specific agreement strategy within a specific agreement featural context. I show that these effects can be captured using Optimality Theory (Prince and Smolensky 2004). The analysis makes use of seven constraints: RES#, MAX[+H], MAX[-H], DEP[-H], MAXNC, DEPNC, and AGREECLOSEST. The hierarchical ranking of these constraints not only accounts for the confinement of particular strategies to specific agreement featural contexts within a language, but also accounts for the cross-linguistic differences in the use of these strategies. I end off by examining the typological implications which follow from the OT analysis provided in this thesis.
- Full Text:
- Date Issued: 2016
- Authors: Mitchley, Hazel
- Date: 2016
- Language: English
- Type: Thesis , Masters , MA
- Identifier: http://hdl.handle.net/10962/3423 , vital:20491
- Description: This thesis provides a unified Optimality Theoretic analysis of subject-verb agreement with coordinated preverbal subjects in three Southern Bantu languages: Xitsonga (S53), Sesotho (S33), and isiXhosa (S41). This analysis is then used to formulate a typology of agreement resolution strategies and the contexts which trigger them. Although some accounts in the Bantu literature suggest that agreement with coordinate structures is avoided by speakers (e.g. Schadeberg 1992, Voeltz 1971) especially when conjuncts are from different noun classes, I show that there is ample evidence to the contrary, and that the subject marker used is dependent on several factors, including (i) the [-HUMAN] specification on the conjuncts, (ii) whether the conjuncts are singular or plural, (iii) whether or not the conjuncts both carry the same noun class feature, and (iv) the order of the conjuncts. This thesis shows that there are various agreement resolution strategies which can beused: 1) agreement with the [+HUMAN] feature on the conjuncts, 2) agreement with the[-HUMAN] feature on the conjuncts, 3) agreement with the noun class feature on both conjuncts, 4) agreement with the noun class feature on the conjunct closest to the verb, and 5) agreement with the noun class feature on the conjunct furthest from the verb. Not all of these strategies are used by all languages, nor are these strategies interchangeable in the languages which do use them – instead, multiple factors conspire to trigger the use of a specific agreement strategy within a specific agreement featural context. I show that these effects can be captured using Optimality Theory (Prince and Smolensky 2004). The analysis makes use of seven constraints: RES#, MAX[+H], MAX[-H], DEP[-H], MAXNC, DEPNC, and AGREECLOSEST. The hierarchical ranking of these constraints not only accounts for the confinement of particular strategies to specific agreement featural contexts within a language, but also accounts for the cross-linguistic differences in the use of these strategies. I end off by examining the typological implications which follow from the OT analysis provided in this thesis.
- Full Text:
- Date Issued: 2016
Advances in platinum-amine chemotherapeutic agents : their chemistry and applicationc
- Authors: Jaganath, Yatish
- Date: 2009
- Subjects: Coordination compounds , Antineoplastic antibiotics , Cancer -- Chemotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10446 , http://hdl.handle.net/10948/d1021222
- Description: The research conducted in this study focussed on advancing the knowledge database of diamineplatinum complexes on two frontiers: 1) the development of novel anticancer complexes, and 2) improvements in their synthetic chemistry. Novel square-planar dichloro and oxalato platinum(II) complexes were synthesized as potential anticancer agents in accordance with a comprehensive set of factors identified as being significant in optimizing such action. The nonleaving ligands consisted of asymmetric chelating chiral diamines of the form 1- (1-R-imidazol-2yl)(R')methanamine (R representing methyl, butyl and R' methyl, phenyl). The complexes were characterized by a host of spectral, thermal and crystallographic techniques. In addition, the stabilities of the complexes were monitored in aqueous and saline solutions. Cytotoxicity screening on three cultured cancer cell lines (MCF-7, HeLa and HT29) indicated the compounds, present as their respective racemates, to have rather modest activities relative to cisplatin; with complexes having the smallest substituents, R,R' = methyl, being most active. In recognition of the limitations of traditional silver-based syntheses of oxalatoplatinum(II) complexes, innovative non-silver methods were developed using the well known cancer drug, oxaliplatin, (trans-R,R-1,2- diaminocyclohexane)oxalatoplatinum(II), as a prototype. These involved direct ligand exchange reactions of the dichloro precursor, (trans-R,R-1,2- diaminocyclohexane)dichloroplatinum(II), with tetrabutylammonium oxalate in essentially non-aqueous solvents. A 90:10 mixture of isoamyl alcohol (3-methyl- 1-butanol):water, proved to be a promising solvent, enabling the recovery of pure oxaliplatin (~98 percent) after 9 hours at 88 °C in yields of up to 86 percent. In light of the perceived unique mode of anticancer action available to mononitroplatinum(IV) complexes (i.e. their STAT3-binding potential), octahedral diamineoxalatoplatinum(IV) complexes containing axially-coordinated nitro and halo co-ligands were synthesized and extensively characterized. Electrochemical studies revealed trends in reduction potential which could be correlated to structural / chemical traits of the coordinated diamine and axial ligands. The similarities of the determined cytotoxicities of the platinum(IV) compounds and their respective platinum(II) analogues, implicated reduction as a means of activation of the platinum(IV) complexes.
- Full Text:
- Date Issued: 2009
- Authors: Jaganath, Yatish
- Date: 2009
- Subjects: Coordination compounds , Antineoplastic antibiotics , Cancer -- Chemotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10446 , http://hdl.handle.net/10948/d1021222
- Description: The research conducted in this study focussed on advancing the knowledge database of diamineplatinum complexes on two frontiers: 1) the development of novel anticancer complexes, and 2) improvements in their synthetic chemistry. Novel square-planar dichloro and oxalato platinum(II) complexes were synthesized as potential anticancer agents in accordance with a comprehensive set of factors identified as being significant in optimizing such action. The nonleaving ligands consisted of asymmetric chelating chiral diamines of the form 1- (1-R-imidazol-2yl)(R')methanamine (R representing methyl, butyl and R' methyl, phenyl). The complexes were characterized by a host of spectral, thermal and crystallographic techniques. In addition, the stabilities of the complexes were monitored in aqueous and saline solutions. Cytotoxicity screening on three cultured cancer cell lines (MCF-7, HeLa and HT29) indicated the compounds, present as their respective racemates, to have rather modest activities relative to cisplatin; with complexes having the smallest substituents, R,R' = methyl, being most active. In recognition of the limitations of traditional silver-based syntheses of oxalatoplatinum(II) complexes, innovative non-silver methods were developed using the well known cancer drug, oxaliplatin, (trans-R,R-1,2- diaminocyclohexane)oxalatoplatinum(II), as a prototype. These involved direct ligand exchange reactions of the dichloro precursor, (trans-R,R-1,2- diaminocyclohexane)dichloroplatinum(II), with tetrabutylammonium oxalate in essentially non-aqueous solvents. A 90:10 mixture of isoamyl alcohol (3-methyl- 1-butanol):water, proved to be a promising solvent, enabling the recovery of pure oxaliplatin (~98 percent) after 9 hours at 88 °C in yields of up to 86 percent. In light of the perceived unique mode of anticancer action available to mononitroplatinum(IV) complexes (i.e. their STAT3-binding potential), octahedral diamineoxalatoplatinum(IV) complexes containing axially-coordinated nitro and halo co-ligands were synthesized and extensively characterized. Electrochemical studies revealed trends in reduction potential which could be correlated to structural / chemical traits of the coordinated diamine and axial ligands. The similarities of the determined cytotoxicities of the platinum(IV) compounds and their respective platinum(II) analogues, implicated reduction as a means of activation of the platinum(IV) complexes.
- Full Text:
- Date Issued: 2009
Reactivity of Rhenium (iii) and Rhenium (V) with multidentate NN-and no-donor ligands
- Yumata, Nonzaliseko Christine
- Authors: Yumata, Nonzaliseko Christine
- Date: 2010
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10373 , http://hdl.handle.net/10948/1085 , Rhenium , Ligands
- Description: The reaction of the potentially tridentate Schiff-base chelate Hhaep [Haep = N’-(1- (2-hydroxyphenyl)ethylidene)benzohydrazide] with [ReCl3(benzil)(PPh3)] and trans-[ReOCl3(PPh3)2] produced the neutral oxorhenium(V) complexes cis- [ReOCl2(mep)] [Hmep = 2-(1-iminoethyl)phenol] and cis-[ReOCI2(meb)(PPh3)] [Hmeb = N’-(propan-2-ylidene)benzohydrazide] in ethanol and acetone respectively. In both reactions the Hhaep molecule cleaves to give different coordinated bidentate NO-donor chelates coordinated to the rhenium(V) centers. The X-ray studies reveal that mep is present as a bidentate, monoanionic Schiffbase coordinating through the neutral imino nitrogen and the deprotonated phenolate oxygen in cis-[ReOCl2(mep)]. The bond distances and angles in cis- [ReOCI2(meb)(PPh3)] confirm that meb coordinates to the metal in the enolate form. The distorted octahedral complex fac-[ReCl3(dpa)(PPh3)] was prepared by the reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of dpa in acetonitrile under a nitrogen atmosphere. The compound dpa.HCl.2H2O was obtained as a by-product in the reaction of dpa with trans-[ReCI3(MeCN)(PPh3)2] in acetonitrile. The reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of 6- amino-3-methyl-1-phenyl-4-azahept-2-ene-1-one (Hamp) in acetonitrile led to the isolation of cis-[ReCl2(bat)(PPh3)2]. On complexation to the metal center Hamp decomposed to give the coordinated benzoylacetone (bat). Bat is present as a monoanionic bidentate chelate. The complexes [ReVOCI(had)] and [ReIVCl(had)(PPh3)](ReO4) were prepared from the reaction of trans-[ReCl3(MeCN)(PPh3)2] with N,N-bis((2-hydroxybenzyl)-2- aminoethyl)dimethylamine (H2had) in ethanol under various reaction conditions. The treatment of [ReCl3(benzil)(PPh3)] with 2-[((2- pyridinylmethyl)amino)methyl]phenol (Hham) in a 2:1 molar ratio in acetonitrile led to the isolation of the hydrogen-bonded dimer [ReOCl2(ham)]2. The distorted octahedral complex [ReOCl(hap)] [H2hap = N,N-bis(2- hydroxybenzyl)aminomethylpyridine] was prepared from the reaction of trans- [ReCl3(MeCN)(PPh3)2] with a twofold molar excess of H2hap in acetonitrile. The X-ray crystal structure analysis shows that the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen.
- Full Text:
- Date Issued: 2010
- Authors: Yumata, Nonzaliseko Christine
- Date: 2010
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10373 , http://hdl.handle.net/10948/1085 , Rhenium , Ligands
- Description: The reaction of the potentially tridentate Schiff-base chelate Hhaep [Haep = N’-(1- (2-hydroxyphenyl)ethylidene)benzohydrazide] with [ReCl3(benzil)(PPh3)] and trans-[ReOCl3(PPh3)2] produced the neutral oxorhenium(V) complexes cis- [ReOCl2(mep)] [Hmep = 2-(1-iminoethyl)phenol] and cis-[ReOCI2(meb)(PPh3)] [Hmeb = N’-(propan-2-ylidene)benzohydrazide] in ethanol and acetone respectively. In both reactions the Hhaep molecule cleaves to give different coordinated bidentate NO-donor chelates coordinated to the rhenium(V) centers. The X-ray studies reveal that mep is present as a bidentate, monoanionic Schiffbase coordinating through the neutral imino nitrogen and the deprotonated phenolate oxygen in cis-[ReOCl2(mep)]. The bond distances and angles in cis- [ReOCI2(meb)(PPh3)] confirm that meb coordinates to the metal in the enolate form. The distorted octahedral complex fac-[ReCl3(dpa)(PPh3)] was prepared by the reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of dpa in acetonitrile under a nitrogen atmosphere. The compound dpa.HCl.2H2O was obtained as a by-product in the reaction of dpa with trans-[ReCI3(MeCN)(PPh3)2] in acetonitrile. The reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of 6- amino-3-methyl-1-phenyl-4-azahept-2-ene-1-one (Hamp) in acetonitrile led to the isolation of cis-[ReCl2(bat)(PPh3)2]. On complexation to the metal center Hamp decomposed to give the coordinated benzoylacetone (bat). Bat is present as a monoanionic bidentate chelate. The complexes [ReVOCI(had)] and [ReIVCl(had)(PPh3)](ReO4) were prepared from the reaction of trans-[ReCl3(MeCN)(PPh3)2] with N,N-bis((2-hydroxybenzyl)-2- aminoethyl)dimethylamine (H2had) in ethanol under various reaction conditions. The treatment of [ReCl3(benzil)(PPh3)] with 2-[((2- pyridinylmethyl)amino)methyl]phenol (Hham) in a 2:1 molar ratio in acetonitrile led to the isolation of the hydrogen-bonded dimer [ReOCl2(ham)]2. The distorted octahedral complex [ReOCl(hap)] [H2hap = N,N-bis(2- hydroxybenzyl)aminomethylpyridine] was prepared from the reaction of trans- [ReCl3(MeCN)(PPh3)2] with a twofold molar excess of H2hap in acetonitrile. The X-ray crystal structure analysis shows that the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen.
- Full Text:
- Date Issued: 2010
The stock identification of the Cape horse mackerel, Trachurus trachurus capensis (Pisces: Carangidae)
- Authors: Naish, Kerry-Ann
- Date: 1990
- Subjects: Carangidae -- Identification , Trachurus trachurus -- Identification , Carangidae -- South Africa , Trachurus trachurus -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5320 , http://hdl.handle.net/10962/d1005165 , Carangidae -- Identification , Trachurus trachurus -- Identification , Carangidae -- South Africa , Trachurus trachurus -- South Africa
- Description: Three stocks of the Cape horse mackerel, Trachurus trachurus capensis, have been recognised in the ICSEAF convention region off southern Africa (Figure 1) on the basis of catch distribution and biological analyses. They were identified as being off Namibia (ICSEAF Divisions 1 . 3 and 1.4), off the West Coast of South Africa (Div. 1.6) and off the South Coast (Div. 2.1 and 2.2). Recently, speculation as to the accuracy of the classification of the South African populations has arisen. The aim of this study was to determine the number of stocks In Divisions 1.6, 2.1 and 2.2, using methodology which assessed the spatial and temporal nature and the phenotypic and genotypic characteristics of the species. The distribution of horse mackerel was evaluated by studying the trends in catch data and length frequency distributions obtained from the demersal industry during 1986 to 1988 and from the demersal biomass cruises in 1987 and 1988. Adult fish, found in Div. 2.1 and 2.2, probably migrated; during the months in which horse mackerel were expected to spawn, CPUE values were higher over the central Agulhas Bank than in the east of the study region. During the quiescent period, catches and numbers were higher in the latter region. Juvenile horse mackerel were found in the nursery areas utilised by pelagic fish and it is likely that they were transported northward from the Agulhas Bank. A decrease in biomass of individuals in Div. 1.5 indicated a separation between a northern and a southern population. Analyses of the phenotype, or epigenetic characters, of horse mackerel were used as a further test of stock integrity. Monthly samples were drawn from Div. 1.6, 2.1 and 2.2 during May 1988 to June, 1989. Comparisons for the values obtained from growth, length-at-50%-maturity and the season of otolith ring formation from each region showed no significant variation in the phenotype. Morphometric analysis proved inconclusive. Monthly gonadosomatic indices show that fish south of the Orange River share the same spawning season. Reports from the literature show that horse mackerel in the latter region differ from those of northern Namibia in spawning season, age-at-50%-maturity and season of otolith ring formation. The genetic structure of the populations of horse mackerel was evaluated by means of a restriction enzyme analysis of the Mitochondrial DNA of 37 fish collected from Divisions 1.4, 1.5, 1.6, 2.1 and 2.2. Two composite genotypes of horse mackerel were found; one belonging to fish in Div. 1.4 and one to fish in Div. 1.6, 2.1 and 2.2. The genetic distance between the two genotypes, 0.07, was the expected distance between two populations at a subspecies level. Fish in Div. 1.5 consisted of both genotypes and may be a region of mixing between the two populations. The interpretation of results was cautioned; prevlous work has shown that the migration of a small number of individuals between two stocks can be expected to maintain a low variation between the populations. In concluding, it was recommended that the horse mackerel be managed as two stocks, one in Div. 1.3 and 1.4 and one in Div. 1.6, 2.1 and 2.2
- Full Text:
- Date Issued: 1990
- Authors: Naish, Kerry-Ann
- Date: 1990
- Subjects: Carangidae -- Identification , Trachurus trachurus -- Identification , Carangidae -- South Africa , Trachurus trachurus -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5320 , http://hdl.handle.net/10962/d1005165 , Carangidae -- Identification , Trachurus trachurus -- Identification , Carangidae -- South Africa , Trachurus trachurus -- South Africa
- Description: Three stocks of the Cape horse mackerel, Trachurus trachurus capensis, have been recognised in the ICSEAF convention region off southern Africa (Figure 1) on the basis of catch distribution and biological analyses. They were identified as being off Namibia (ICSEAF Divisions 1 . 3 and 1.4), off the West Coast of South Africa (Div. 1.6) and off the South Coast (Div. 2.1 and 2.2). Recently, speculation as to the accuracy of the classification of the South African populations has arisen. The aim of this study was to determine the number of stocks In Divisions 1.6, 2.1 and 2.2, using methodology which assessed the spatial and temporal nature and the phenotypic and genotypic characteristics of the species. The distribution of horse mackerel was evaluated by studying the trends in catch data and length frequency distributions obtained from the demersal industry during 1986 to 1988 and from the demersal biomass cruises in 1987 and 1988. Adult fish, found in Div. 2.1 and 2.2, probably migrated; during the months in which horse mackerel were expected to spawn, CPUE values were higher over the central Agulhas Bank than in the east of the study region. During the quiescent period, catches and numbers were higher in the latter region. Juvenile horse mackerel were found in the nursery areas utilised by pelagic fish and it is likely that they were transported northward from the Agulhas Bank. A decrease in biomass of individuals in Div. 1.5 indicated a separation between a northern and a southern population. Analyses of the phenotype, or epigenetic characters, of horse mackerel were used as a further test of stock integrity. Monthly samples were drawn from Div. 1.6, 2.1 and 2.2 during May 1988 to June, 1989. Comparisons for the values obtained from growth, length-at-50%-maturity and the season of otolith ring formation from each region showed no significant variation in the phenotype. Morphometric analysis proved inconclusive. Monthly gonadosomatic indices show that fish south of the Orange River share the same spawning season. Reports from the literature show that horse mackerel in the latter region differ from those of northern Namibia in spawning season, age-at-50%-maturity and season of otolith ring formation. The genetic structure of the populations of horse mackerel was evaluated by means of a restriction enzyme analysis of the Mitochondrial DNA of 37 fish collected from Divisions 1.4, 1.5, 1.6, 2.1 and 2.2. Two composite genotypes of horse mackerel were found; one belonging to fish in Div. 1.4 and one to fish in Div. 1.6, 2.1 and 2.2. The genetic distance between the two genotypes, 0.07, was the expected distance between two populations at a subspecies level. Fish in Div. 1.5 consisted of both genotypes and may be a region of mixing between the two populations. The interpretation of results was cautioned; prevlous work has shown that the migration of a small number of individuals between two stocks can be expected to maintain a low variation between the populations. In concluding, it was recommended that the horse mackerel be managed as two stocks, one in Div. 1.3 and 1.4 and one in Div. 1.6, 2.1 and 2.2
- Full Text:
- Date Issued: 1990
Solvent-free synthesis of bisferrocenylimines and their coordination to rhodium (I)
- Authors: Kleyi, Phumelele Eldridge
- Date: 2009
- Subjects: Organic compounds -- Synthesis , Organic solvents , Solution (Chemistry) , Chemistry, Organic , Coordination compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10393 , http://hdl.handle.net/10948/1053 , Organic compounds -- Synthesis , Organic solvents , Solution (Chemistry) , Chemistry, Organic , Coordination compounds
- Description: Solvent-free reactions possess advantages compared to the solvent route, such as shorter reaction times, less use of energy, better yields, etc. Herein, the synthesis and characterization of bisferrocenylimines and arylbisamines are described. Reduction of the above compounds with LAH resulted in the formation of bisferrocenylamines and arylbisamines, respectively. The coordination chemistry of all the above compounds to rhodium(I) is also discussed in the prepared complexes [Rh(COD)(NN)]ClO4, where NN = bisferrocenylimines, and [Rh(COD)(NN)]BF4, where NN = bisferrocenylamines and arylbisamines. X-ray crystal structures of the complexes [Rh(COD)(NN)]ClO4 ([3.2] and [3.3]) have been obtained. Complexes of the type [Rh(COD)(NN)]BF4 were characterized with IR and UV-vis spectroscopy, cyclic voltammetry and conductometry. The catalytic activity of the complexes was also investigated: [Rh(COD)(NN)]ClO4 for the polymerization of phenylacetylene and [Rh(COD)(NN)]BF4 for the hydroformylation of styrene.
- Full Text:
- Date Issued: 2009
- Authors: Kleyi, Phumelele Eldridge
- Date: 2009
- Subjects: Organic compounds -- Synthesis , Organic solvents , Solution (Chemistry) , Chemistry, Organic , Coordination compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10393 , http://hdl.handle.net/10948/1053 , Organic compounds -- Synthesis , Organic solvents , Solution (Chemistry) , Chemistry, Organic , Coordination compounds
- Description: Solvent-free reactions possess advantages compared to the solvent route, such as shorter reaction times, less use of energy, better yields, etc. Herein, the synthesis and characterization of bisferrocenylimines and arylbisamines are described. Reduction of the above compounds with LAH resulted in the formation of bisferrocenylamines and arylbisamines, respectively. The coordination chemistry of all the above compounds to rhodium(I) is also discussed in the prepared complexes [Rh(COD)(NN)]ClO4, where NN = bisferrocenylimines, and [Rh(COD)(NN)]BF4, where NN = bisferrocenylamines and arylbisamines. X-ray crystal structures of the complexes [Rh(COD)(NN)]ClO4 ([3.2] and [3.3]) have been obtained. Complexes of the type [Rh(COD)(NN)]BF4 were characterized with IR and UV-vis spectroscopy, cyclic voltammetry and conductometry. The catalytic activity of the complexes was also investigated: [Rh(COD)(NN)]ClO4 for the polymerization of phenylacetylene and [Rh(COD)(NN)]BF4 for the hydroformylation of styrene.
- Full Text:
- Date Issued: 2009
Rhenium complexes of benzazole derivatives
- Authors: Van Niekerk, Xandri
- Date: 2017
- Subjects: Rhenium Benzimidazoles
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/21252 , vital:29467
- Description: A series of rhenium(I) complexes with monodentate benzazole ligands containing the fac-[Re(CO)3]+ was synthesized. The rhenium(I) compound [ReCl(Hmbt)2(CO)3] was prepared from the reaction of [Re(CO)5Cl] and 2-aminobenzothiazole (Hmbt) in toluene. The ligand coordinates in a monodentate manner via the thiazole nitrogen atom. A similar reaction between [Re(CO)5Cl] and N-(1,3-benzothiazol-2-yl)-2- chloroacetamide (Hbct) resulted in the formation of [ReCl(Hbct)(CO)3(NCMe)], where only one ligand binds per rhenium in a monodentate fashion. The reaction of ligands 2-mercaptobenzimidazole (Hmbi) (dibenzothiazol-2-yl)tetraazathiapentalene (Hdbt) with rhenium(I) gave [ReCl(Hmbi)2(CO)3] and [ReCl(Hdbt)2(CO)3] respectively. The study on the coordination behaviour between ethyl-(1H-benzimidazol-2-yl-sulfanyl) acetate (Hbsa) and [Re(CO)5Cl] surprisingly gave the dimeric species (μ-Cl)2[Re(Hbsa)(CO)3]2, where the two rhenium atoms are bridged by two chloro ligands. The coordination of Hbsa occurs through the imidazole nitrogen, leaving the ethoxy tail free on each Hbsa ligand. The coordination behaviour of benzimidazole and benzothiazole derivatives gave rhenium complexes in oxidation states I, III and V, where all the ligands coordinate as bidentate N,N-chelating ligands. The study on 2-(2-aminophenyl)-1-benzothiazole (Hapt) and 2-(2-aminophenyl)-1-benzimidazole (H2apz) with [ReVOCl3(PPh3)2] resulted in the formation of [ReVOCl2(apt)(OPPh3)] and [ReVCl2(apz)(PPh3)2](ReO4), respectively. 1,2-Bis(2-benzimidazole)-1,2-ethanediol (Hbed) and 2,6-bis(2- benzimidazol-2-yl)pyridine (H2bip) were studied towards rhenium(I) and rheniumV) respectively. The former gave a dimeric species (μ-bbi)[Re(CO)4]2 (H2bbi – bisbenzimidazole) by reaction with [Re(CO)5Cl], whereas H2bip produced the rhenium(III) cationic salt [ReCl3(H3bip)(PPh3)]Cl, where the ligand coordinates as a cationic H3bip+ with protonation of an uncoordinated imidazole nitrogen atom. The pyridine derivatives 2-hydrazino-pyridinyl-2-benzothiazole (Hhpt) and (E)-1-benzo[d]thiazol-2-yl)-2- (pyridin-2-ylmethylene)hydrazine (btp) were reacted with [Re(CO)5Cl]. The neutral complex [ReCl(Hhpt)(CO)3] was isolated upon reaction with Hhpt, where Hhpt coordinates as a neutral bidentate ligand. The reaction of [Re(CO)5Cl] with btp gave two different complexes when using different solvents. In methanol, [ReCl(btp)(CO)3] was isolated, whereas in toluene, the conjugate of btp (btp1) was formed which resulted in the formation of [ReCl(btp1)(CO)3]. The study on potentially bidentate thiourea derivatives containing a benzothiazole moiety towards [ReI(CO)3]+ and [ReVO]3+ cores gave rise to a wide variety of complexes. The reaction of [Re(CO)5Cl] with N-phenyl-N-(2-benzothiazole)thiourea (Hpbt) produced the rhenium(I) complex [Re(Hpbt)(pbt)(CO)3]. Hpbt coordinates both as a monodentate neutral ligand and as a bidentate monoanionic chelate. The study of the reaction between trans-[ReOCl3(PPh3)2] and Hpbt gave the rhenium(V) product [ReOCl2(pbt)(PPh3)], with pbt acting as a bidentate ligand. The reaction of 1-(1,3- benzothiazol-2-yl)-3-benzoylthiourea (Hbbt) with [Re(CO)5Cl] led to the isolation of [ReCl(Hbbt)(CO)3]. Similar reaction of Hbbt with trans-[ReOCl3(PPh3)2] gave the unique compound [ReOCl2(Hbnt)(PPh3)], where the ligand coordinates via the ketonic oxygen and a methine carbon. The complex [Re(Hmby)(mby)(CO)3] was isolated upon reacting [Re(CO)5Cl] with methylbenzothiazol-2-ylidenecarbamodithioate (Hmby), with Hmby coordinating as a monodentate neutral ligand and mby as a bidentate monoanionic chelate. The coordination behaviour of N-(benzothiazol-2-yl)-S,S’- dimethyldithiocarboimine (Hbdc) towards rhenium(I) led to the formation of [ReCl(Hbdc)(CO)3]. The reactivity of 1-(benzothiozol-2-yl)-3,3-dimethylthiourea (Hbdm), a derivative of Hmby, was studied with trans-[ReOCl3(PPh3)2] and trans- [ReO(OEt)I2(PPh3)2] producing the square pyramidal compound [ReOCl(bdm)2] and the salt [Re(bdm)2(MeCN)2]I3, respectively. Pyrazole derivatives containing a benzothiazole ring were studied towards rhenium in oxidation states +I and +V. The reaction between 2-(3,5-dimethylpyrazol-1-yl)benzothiazole (Hdmp) and [Re(CO)5Cl] gave the neutral rhenium complex [ReCl(Hdmp)(CO)3], whereas its reaction with [ReOCl3(PPh3)2] surprisingly results in the formation of a dimeric complex (μ-O)[ReOCl2(Hdmp)]2. The study on the reactivity of 1-(benzo[d]thiazol-2-yl)-4-methyl-1H-pyrrol-2-ol (Hbtm) with [Re(CO)5Cl] gave the unexpected trimer [Re(btm)(CO)3]3 containing the fac-[Re(CO)3]+ core. The ligand btm forms a bridge between each rhenium metal, serving as a bidentate ligand to one rhenium, and a monodentate ligand to another rhenium atom. The study on the coordination chemistry between trans-[ReOCl3(PPh3)2] and Hbtm gave two different complexes when using different solvents. In ethanol, [ReOCl(btm)(btm1)] formed, whereas [ReOCl(btm1)(btz)] (Hbtz = 1-(benzo[d]thiazol-2-yl)-4-(1-iminoethyl)-3- methyl-1H-pyrazol-5-ol) was isolated in acetonitrile. The reaction of cis-[ReO2I(PPh3)2] also gave two different products when using different solvents, where the respective solvents coordinate to the metal. The rhenium(V) compound [ReO(OMe)(btm)(btm1)] was formed in methanol, whereas [ReO(OEt)(btm)(btm1)] was formed in ethanol. The coordination chemistry of 2-(2-Benzothiazoleyl)-4,5,6,7-tetrahydro-2H-indazol-3-ol (Hbth) was studied towards [Re(CO)5Cl] and trans-[ReOCl3(PPh3)2]. The resulting complexes which formed are [ReCl(Hbth)(CO)3] and [ReOCl(bth)(bth1)] respectively. The reactivity of potentially tridentate Schiff base ligands towards rhenium(I) and (V) was studied. The rhenium(I) precursor [Re(CO)5Cl] was reacted with (E)-1- (benzo[d]thiazol-2-yl)-2-(phenol-2-ylmethylene)hydrazine (H3bph) to give [ReCl(CO)3(H3bph)], which contains the kinetically inert fac-[Re(CO)3]+ core coordinated to a neutral bidentate ligand. The reaction of [ReO2(py)4Cl] with H3bph gave the dimeric species (μ-O)[ReO(Hbph)(py)]2, where the ligand coordinates as a tridentate dianionic chelate. A similar complex was isolated with (E)-1- (benzo[d]thiazol-2-yl)-2-(2,4-dihydroxy-2-ylmethylene)hydrazine (H3bdh) to give (μ-O)[ReO(Hbdh)(py)]2. The reaction of trans-[ReOCl3(PPh3)2] with H3bph afforded [Re(abt)(imp)Cl2(PPh3)] (abt = 2-aminobenzothiazole, imp = 2-(iminomethyl)phenol), where the ligand broke up into two fragments, both of which coordinated without any modification. The dioxo rhenium precursor cis-[ReO2I(PPh3)2] gave [ReO(Hbdh)(imp)] upon reaction with H3bdh. Ligand imp coordinates as a bidentate monoanionic ligand via the imine nitrogen and deprotonated phenolic oxygen and ligand Hbdh coordinatesas a tridentate dianionic chelate.
- Full Text:
- Date Issued: 2017
- Authors: Van Niekerk, Xandri
- Date: 2017
- Subjects: Rhenium Benzimidazoles
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/21252 , vital:29467
- Description: A series of rhenium(I) complexes with monodentate benzazole ligands containing the fac-[Re(CO)3]+ was synthesized. The rhenium(I) compound [ReCl(Hmbt)2(CO)3] was prepared from the reaction of [Re(CO)5Cl] and 2-aminobenzothiazole (Hmbt) in toluene. The ligand coordinates in a monodentate manner via the thiazole nitrogen atom. A similar reaction between [Re(CO)5Cl] and N-(1,3-benzothiazol-2-yl)-2- chloroacetamide (Hbct) resulted in the formation of [ReCl(Hbct)(CO)3(NCMe)], where only one ligand binds per rhenium in a monodentate fashion. The reaction of ligands 2-mercaptobenzimidazole (Hmbi) (dibenzothiazol-2-yl)tetraazathiapentalene (Hdbt) with rhenium(I) gave [ReCl(Hmbi)2(CO)3] and [ReCl(Hdbt)2(CO)3] respectively. The study on the coordination behaviour between ethyl-(1H-benzimidazol-2-yl-sulfanyl) acetate (Hbsa) and [Re(CO)5Cl] surprisingly gave the dimeric species (μ-Cl)2[Re(Hbsa)(CO)3]2, where the two rhenium atoms are bridged by two chloro ligands. The coordination of Hbsa occurs through the imidazole nitrogen, leaving the ethoxy tail free on each Hbsa ligand. The coordination behaviour of benzimidazole and benzothiazole derivatives gave rhenium complexes in oxidation states I, III and V, where all the ligands coordinate as bidentate N,N-chelating ligands. The study on 2-(2-aminophenyl)-1-benzothiazole (Hapt) and 2-(2-aminophenyl)-1-benzimidazole (H2apz) with [ReVOCl3(PPh3)2] resulted in the formation of [ReVOCl2(apt)(OPPh3)] and [ReVCl2(apz)(PPh3)2](ReO4), respectively. 1,2-Bis(2-benzimidazole)-1,2-ethanediol (Hbed) and 2,6-bis(2- benzimidazol-2-yl)pyridine (H2bip) were studied towards rhenium(I) and rheniumV) respectively. The former gave a dimeric species (μ-bbi)[Re(CO)4]2 (H2bbi – bisbenzimidazole) by reaction with [Re(CO)5Cl], whereas H2bip produced the rhenium(III) cationic salt [ReCl3(H3bip)(PPh3)]Cl, where the ligand coordinates as a cationic H3bip+ with protonation of an uncoordinated imidazole nitrogen atom. The pyridine derivatives 2-hydrazino-pyridinyl-2-benzothiazole (Hhpt) and (E)-1-benzo[d]thiazol-2-yl)-2- (pyridin-2-ylmethylene)hydrazine (btp) were reacted with [Re(CO)5Cl]. The neutral complex [ReCl(Hhpt)(CO)3] was isolated upon reaction with Hhpt, where Hhpt coordinates as a neutral bidentate ligand. The reaction of [Re(CO)5Cl] with btp gave two different complexes when using different solvents. In methanol, [ReCl(btp)(CO)3] was isolated, whereas in toluene, the conjugate of btp (btp1) was formed which resulted in the formation of [ReCl(btp1)(CO)3]. The study on potentially bidentate thiourea derivatives containing a benzothiazole moiety towards [ReI(CO)3]+ and [ReVO]3+ cores gave rise to a wide variety of complexes. The reaction of [Re(CO)5Cl] with N-phenyl-N-(2-benzothiazole)thiourea (Hpbt) produced the rhenium(I) complex [Re(Hpbt)(pbt)(CO)3]. Hpbt coordinates both as a monodentate neutral ligand and as a bidentate monoanionic chelate. The study of the reaction between trans-[ReOCl3(PPh3)2] and Hpbt gave the rhenium(V) product [ReOCl2(pbt)(PPh3)], with pbt acting as a bidentate ligand. The reaction of 1-(1,3- benzothiazol-2-yl)-3-benzoylthiourea (Hbbt) with [Re(CO)5Cl] led to the isolation of [ReCl(Hbbt)(CO)3]. Similar reaction of Hbbt with trans-[ReOCl3(PPh3)2] gave the unique compound [ReOCl2(Hbnt)(PPh3)], where the ligand coordinates via the ketonic oxygen and a methine carbon. The complex [Re(Hmby)(mby)(CO)3] was isolated upon reacting [Re(CO)5Cl] with methylbenzothiazol-2-ylidenecarbamodithioate (Hmby), with Hmby coordinating as a monodentate neutral ligand and mby as a bidentate monoanionic chelate. The coordination behaviour of N-(benzothiazol-2-yl)-S,S’- dimethyldithiocarboimine (Hbdc) towards rhenium(I) led to the formation of [ReCl(Hbdc)(CO)3]. The reactivity of 1-(benzothiozol-2-yl)-3,3-dimethylthiourea (Hbdm), a derivative of Hmby, was studied with trans-[ReOCl3(PPh3)2] and trans- [ReO(OEt)I2(PPh3)2] producing the square pyramidal compound [ReOCl(bdm)2] and the salt [Re(bdm)2(MeCN)2]I3, respectively. Pyrazole derivatives containing a benzothiazole ring were studied towards rhenium in oxidation states +I and +V. The reaction between 2-(3,5-dimethylpyrazol-1-yl)benzothiazole (Hdmp) and [Re(CO)5Cl] gave the neutral rhenium complex [ReCl(Hdmp)(CO)3], whereas its reaction with [ReOCl3(PPh3)2] surprisingly results in the formation of a dimeric complex (μ-O)[ReOCl2(Hdmp)]2. The study on the reactivity of 1-(benzo[d]thiazol-2-yl)-4-methyl-1H-pyrrol-2-ol (Hbtm) with [Re(CO)5Cl] gave the unexpected trimer [Re(btm)(CO)3]3 containing the fac-[Re(CO)3]+ core. The ligand btm forms a bridge between each rhenium metal, serving as a bidentate ligand to one rhenium, and a monodentate ligand to another rhenium atom. The study on the coordination chemistry between trans-[ReOCl3(PPh3)2] and Hbtm gave two different complexes when using different solvents. In ethanol, [ReOCl(btm)(btm1)] formed, whereas [ReOCl(btm1)(btz)] (Hbtz = 1-(benzo[d]thiazol-2-yl)-4-(1-iminoethyl)-3- methyl-1H-pyrazol-5-ol) was isolated in acetonitrile. The reaction of cis-[ReO2I(PPh3)2] also gave two different products when using different solvents, where the respective solvents coordinate to the metal. The rhenium(V) compound [ReO(OMe)(btm)(btm1)] was formed in methanol, whereas [ReO(OEt)(btm)(btm1)] was formed in ethanol. The coordination chemistry of 2-(2-Benzothiazoleyl)-4,5,6,7-tetrahydro-2H-indazol-3-ol (Hbth) was studied towards [Re(CO)5Cl] and trans-[ReOCl3(PPh3)2]. The resulting complexes which formed are [ReCl(Hbth)(CO)3] and [ReOCl(bth)(bth1)] respectively. The reactivity of potentially tridentate Schiff base ligands towards rhenium(I) and (V) was studied. The rhenium(I) precursor [Re(CO)5Cl] was reacted with (E)-1- (benzo[d]thiazol-2-yl)-2-(phenol-2-ylmethylene)hydrazine (H3bph) to give [ReCl(CO)3(H3bph)], which contains the kinetically inert fac-[Re(CO)3]+ core coordinated to a neutral bidentate ligand. The reaction of [ReO2(py)4Cl] with H3bph gave the dimeric species (μ-O)[ReO(Hbph)(py)]2, where the ligand coordinates as a tridentate dianionic chelate. A similar complex was isolated with (E)-1- (benzo[d]thiazol-2-yl)-2-(2,4-dihydroxy-2-ylmethylene)hydrazine (H3bdh) to give (μ-O)[ReO(Hbdh)(py)]2. The reaction of trans-[ReOCl3(PPh3)2] with H3bph afforded [Re(abt)(imp)Cl2(PPh3)] (abt = 2-aminobenzothiazole, imp = 2-(iminomethyl)phenol), where the ligand broke up into two fragments, both of which coordinated without any modification. The dioxo rhenium precursor cis-[ReO2I(PPh3)2] gave [ReO(Hbdh)(imp)] upon reaction with H3bdh. Ligand imp coordinates as a bidentate monoanionic ligand via the imine nitrogen and deprotonated phenolic oxygen and ligand Hbdh coordinatesas a tridentate dianionic chelate.
- Full Text:
- Date Issued: 2017
Effect of lipid inclusion levels in aquafeed on carcass composition, quality change during storage and nutrient excretion in dusky kob (Argyrosomus japonicus)
- Authors: Ginindza, Nhlanhla Joseph
- Date: 2016
- Subjects: Aquaculture
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5387 , http://hdl.handle.net/10962/d1020854
- Description: Dusky kob, Argyrosomus japonicus, is an aquaculture species in South Africa that is in pilot commercial production. While the major nutrient requirements of the species are known, the advantages of incorporating formulated feeds into the diet of the species has yet to be fully explored. Research on formulated feed composition is required to: minimise input costs; improve the organoleptic properties and meat quality; and minimise nutrient loss, which contributes to environmental pollution. This study sought to test the impact of different lipid levels in aquafeeds fed to dusky kob juveniles by determining: (i) growth performance, feeding efficiency, proximate and fatty acid composition; (ii) chemical changes and shelf-life of refrigerated fish fillets; and (iii) metabolic rates and nitrogen excretion of juvenile dusky kob. And more...
- Full Text:
- Date Issued: 2016
- Authors: Ginindza, Nhlanhla Joseph
- Date: 2016
- Subjects: Aquaculture
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5387 , http://hdl.handle.net/10962/d1020854
- Description: Dusky kob, Argyrosomus japonicus, is an aquaculture species in South Africa that is in pilot commercial production. While the major nutrient requirements of the species are known, the advantages of incorporating formulated feeds into the diet of the species has yet to be fully explored. Research on formulated feed composition is required to: minimise input costs; improve the organoleptic properties and meat quality; and minimise nutrient loss, which contributes to environmental pollution. This study sought to test the impact of different lipid levels in aquafeeds fed to dusky kob juveniles by determining: (i) growth performance, feeding efficiency, proximate and fatty acid composition; (ii) chemical changes and shelf-life of refrigerated fish fillets; and (iii) metabolic rates and nitrogen excretion of juvenile dusky kob. And more...
- Full Text:
- Date Issued: 2016
The coordination chemistry of Rhenium(V) with multidentate no-donor ligands
- Authors: Abrahams, Abubak'r
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10370 , http://hdl.handle.net/10948/912 , Rhenium , Ligands
- Description: The neutral distorted octahedral complexes [ReOCl(L)] {H2L = N,N-bis(2- hydroxybenzyl)-2-(2-aminoethyl)dimethylamine (H2had), N,N-bis(2-hydroxybenzyl) aminomethylpyridine (H2hap); N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)pyridine (H2hae)} were prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H2L in ethanol. The X-ray structure determinations of [ReOCl(had)] and [ReOCl(hap)] were performed, and in both complexes the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen. Treatment of trans-[ReO2(py)4]I with two equivalents and one equivalent each of H2had in acetone afforded the iodide salts of the oxypyridinium-ammonium zwitterions N1-(2-hydroxybenzyl)-N2,N2- dimethyl-N1-((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [Hhpd]+ and N2,N2- dimethyl-N1-bis((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [dod]+ respectively. In [Hhpd]I, one of the 2-hydroxyphenyl groups of H2had is substituted by an oxypyridinium group, and in [dod]I, both 2-hydroxyphenyl groups are converted. The X-ray crystal structure determination of the starting material H2had, [Hhpd]I and [dod]I reveals trigonal pyramidal geometries around the central amino nitrogen. The complex salt [ReO(bsa)]PF6 (H2bsa=bis(N-methylsalicylicylideneiminopropyl) amine) was prepared from the reaction of cis-[ReO2I(PPh3)2] with H2bsa in toluene. The dianionic pentadentate ligand bsa is coordinated to the ReO3+ moiety via one secondary amino and two imino nitrogens, and two anionic phenolate oxygens. The complex was characterized by spectroscopy and analytical data, and the structure has been determined by single-crystal X-ray diffraction analysis. The complex exhibits a distorted octahedral geometry around the central rhenium(V) ion, with the basal plane being defined by a phenolate oxygen, two imino nitrogens and the secondary amino. ix A. Abrahams Nelson Mandela Metropolitan University The reaction of a two-fold molar excess of the potentially NN-donor ligand 2,2’- dipyridylamine (dpa) with trans-[ReO(OEt)Cl2(PPh3)2] in ethanol led to the isolation of [ReOCl2(OEt)(dpa)]. The X-ray crystal structure shows that the NN-chelated dpa is coordinated in the equatorial plane cis to the oxo and ethoxo groups, which are in trans positions relative to each other. The treatment of trans- [ReOCl3(PPh3)2] with a tenfold molar excess of dpa in ethanol at the refluxing temperature yielded the trans-dioxo complex [ReO2(dpa)2]Cl, but with a twofold molar excess only (μ-O)[{ReOCl2(dpa)}2] was isolated. Repeating the latter reaction with (n-Bu4N)[ReOCl4] as starting material in ethanol at room temperature a dark green product, also with the formulation (μ-O)[{ReOCl2(dpa)}2], was isolated. The reaction of equimolar quantities of bis(pyridin-2-yl)methyl)amine (HBPA) with (n-Bu4N)[ReOCl4] in acetone at room temperature led to the isolation of the sixcoordinate rhenium(V) complex [ReOCl(H2O)(BPA)]Cl. IR, NMR and X-ray crystallographic results indicate that BPA is coordinated as a tridentate uninegative chelate, with deprotonation of the amine nitrogen. The water molecule is coordinated trans to the oxo group, with the Re=O and Re-OH2 bond distances equal to 1.663(9) and 2.21(1) Å respectively. Complexes of the general formula [ReOX2{(C5H4N)CH(O)CH2(C5H4N)}] (X = Cl, I) were prepared by the reactions of trans-[ReOCl3(PPh3)2] and trans- [ReOI2(OEt)(PPh3)2] with cis-1,2-di-(2-pyridyl)ethylene (DPE) in ethanol and benzene in air. Experimental evidence shows that the coordinated DPE ligand has undergone addition of water at the ethylenic carbons, and that the (C5H4N)CH(O)CH2(C5H4N) moiety acts as a uninegative tridentate NON-donor ligand. The X-ray crystal structures of both complexes show a distorted octahedral geometry around the rhenium(V) centre. The treatment of trans-[ReOCl3(PPh3)2] with H2dbd in a 2:1 molar ratio in acetonitrile led to the isolation of the ligand-bridged dimer (μ-dbd)[ReOCl2(PPh3)]2. The X-ray crystal structure of the complex reveals a dinuclear structure in which two rhenium(V) ions are bridged by the dbd ligand. Each rhenium ion is in a x A. Abrahams Nelson Mandela Metropolitan University distorted octahedral geometry. The basal plane is defined by a phosphorus atom of the PPh3 group, two chlorides cis to each other, and a pyridyl nitrogen atom of dbd. The oxo group and alcoholate oxygen of dbd lie in trans axial positions. The complexes cis-[ReOX2(msa)(PPh3)] (X = Cl, Br, I) were prepared from trans- [ReOCl3(PPh3)2], trans-[ReOBr3(PPh3)2] or trans-[ReOI2(OEt)(PPh3)2] with 2-(1- iminoethyl)phenol (Hmsa) in acetonitrile. An X-ray crystallographic study shows that the bonding distances and angles in the comlexes are nearly identical, and that the two halides in each complex are coordinated cis to each other in the equatorial plane cis to the oxo group. The oxo-bridged dinuclear rhenium(V) complex [(μ-O){ReOCl(amp)}2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] and 6-amino-3-methyl-1-phenyl- 4-azahept-2-ene-1-one (Hamp) in acetone. The characterization of the complex by elemental analysis, infrared and 1H NMR spectroscopy and X-ray crystallography shows that amp is coordinated as a monoanionic NNO-donor chelate as an amino-amido ketone. However, the reaction of the similar ligand 7- amino-4,7-dimethyl-5-aza-3-octen-2-one (Hada) with [Re(CO)5Br] produced the product fac-[Re(CO)3Br(Hada)], with Hada coordinated as a neutral NN-donor amino-imino-ketone.
- Full Text:
- Date Issued: 2009
- Authors: Abrahams, Abubak'r
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10370 , http://hdl.handle.net/10948/912 , Rhenium , Ligands
- Description: The neutral distorted octahedral complexes [ReOCl(L)] {H2L = N,N-bis(2- hydroxybenzyl)-2-(2-aminoethyl)dimethylamine (H2had), N,N-bis(2-hydroxybenzyl) aminomethylpyridine (H2hap); N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)pyridine (H2hae)} were prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H2L in ethanol. The X-ray structure determinations of [ReOCl(had)] and [ReOCl(hap)] were performed, and in both complexes the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen. Treatment of trans-[ReO2(py)4]I with two equivalents and one equivalent each of H2had in acetone afforded the iodide salts of the oxypyridinium-ammonium zwitterions N1-(2-hydroxybenzyl)-N2,N2- dimethyl-N1-((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [Hhpd]+ and N2,N2- dimethyl-N1-bis((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [dod]+ respectively. In [Hhpd]I, one of the 2-hydroxyphenyl groups of H2had is substituted by an oxypyridinium group, and in [dod]I, both 2-hydroxyphenyl groups are converted. The X-ray crystal structure determination of the starting material H2had, [Hhpd]I and [dod]I reveals trigonal pyramidal geometries around the central amino nitrogen. The complex salt [ReO(bsa)]PF6 (H2bsa=bis(N-methylsalicylicylideneiminopropyl) amine) was prepared from the reaction of cis-[ReO2I(PPh3)2] with H2bsa in toluene. The dianionic pentadentate ligand bsa is coordinated to the ReO3+ moiety via one secondary amino and two imino nitrogens, and two anionic phenolate oxygens. The complex was characterized by spectroscopy and analytical data, and the structure has been determined by single-crystal X-ray diffraction analysis. The complex exhibits a distorted octahedral geometry around the central rhenium(V) ion, with the basal plane being defined by a phenolate oxygen, two imino nitrogens and the secondary amino. ix A. Abrahams Nelson Mandela Metropolitan University The reaction of a two-fold molar excess of the potentially NN-donor ligand 2,2’- dipyridylamine (dpa) with trans-[ReO(OEt)Cl2(PPh3)2] in ethanol led to the isolation of [ReOCl2(OEt)(dpa)]. The X-ray crystal structure shows that the NN-chelated dpa is coordinated in the equatorial plane cis to the oxo and ethoxo groups, which are in trans positions relative to each other. The treatment of trans- [ReOCl3(PPh3)2] with a tenfold molar excess of dpa in ethanol at the refluxing temperature yielded the trans-dioxo complex [ReO2(dpa)2]Cl, but with a twofold molar excess only (μ-O)[{ReOCl2(dpa)}2] was isolated. Repeating the latter reaction with (n-Bu4N)[ReOCl4] as starting material in ethanol at room temperature a dark green product, also with the formulation (μ-O)[{ReOCl2(dpa)}2], was isolated. The reaction of equimolar quantities of bis(pyridin-2-yl)methyl)amine (HBPA) with (n-Bu4N)[ReOCl4] in acetone at room temperature led to the isolation of the sixcoordinate rhenium(V) complex [ReOCl(H2O)(BPA)]Cl. IR, NMR and X-ray crystallographic results indicate that BPA is coordinated as a tridentate uninegative chelate, with deprotonation of the amine nitrogen. The water molecule is coordinated trans to the oxo group, with the Re=O and Re-OH2 bond distances equal to 1.663(9) and 2.21(1) Å respectively. Complexes of the general formula [ReOX2{(C5H4N)CH(O)CH2(C5H4N)}] (X = Cl, I) were prepared by the reactions of trans-[ReOCl3(PPh3)2] and trans- [ReOI2(OEt)(PPh3)2] with cis-1,2-di-(2-pyridyl)ethylene (DPE) in ethanol and benzene in air. Experimental evidence shows that the coordinated DPE ligand has undergone addition of water at the ethylenic carbons, and that the (C5H4N)CH(O)CH2(C5H4N) moiety acts as a uninegative tridentate NON-donor ligand. The X-ray crystal structures of both complexes show a distorted octahedral geometry around the rhenium(V) centre. The treatment of trans-[ReOCl3(PPh3)2] with H2dbd in a 2:1 molar ratio in acetonitrile led to the isolation of the ligand-bridged dimer (μ-dbd)[ReOCl2(PPh3)]2. The X-ray crystal structure of the complex reveals a dinuclear structure in which two rhenium(V) ions are bridged by the dbd ligand. Each rhenium ion is in a x A. Abrahams Nelson Mandela Metropolitan University distorted octahedral geometry. The basal plane is defined by a phosphorus atom of the PPh3 group, two chlorides cis to each other, and a pyridyl nitrogen atom of dbd. The oxo group and alcoholate oxygen of dbd lie in trans axial positions. The complexes cis-[ReOX2(msa)(PPh3)] (X = Cl, Br, I) were prepared from trans- [ReOCl3(PPh3)2], trans-[ReOBr3(PPh3)2] or trans-[ReOI2(OEt)(PPh3)2] with 2-(1- iminoethyl)phenol (Hmsa) in acetonitrile. An X-ray crystallographic study shows that the bonding distances and angles in the comlexes are nearly identical, and that the two halides in each complex are coordinated cis to each other in the equatorial plane cis to the oxo group. The oxo-bridged dinuclear rhenium(V) complex [(μ-O){ReOCl(amp)}2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] and 6-amino-3-methyl-1-phenyl- 4-azahept-2-ene-1-one (Hamp) in acetone. The characterization of the complex by elemental analysis, infrared and 1H NMR spectroscopy and X-ray crystallography shows that amp is coordinated as a monoanionic NNO-donor chelate as an amino-amido ketone. However, the reaction of the similar ligand 7- amino-4,7-dimethyl-5-aza-3-octen-2-one (Hada) with [Re(CO)5Br] produced the product fac-[Re(CO)3Br(Hada)], with Hada coordinated as a neutral NN-donor amino-imino-ketone.
- Full Text:
- Date Issued: 2009
Characterization and electrocatalytic applications of metallophthalocyanine-single walled carbon nanotube conjugates
- Authors: Mugadza, Tawanda
- Date: 2011 , 2011-03-30
- Subjects: Phthalocyanines Pesticides Nanotubes Electrocatalysis Electrochemistry Transmission electron microscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4419 , http://hdl.handle.net/10962/d1006855
- Description: Metallophthalocyanine-single walled carbon nanotube conjugates were successfully synthesized and applied in the electrochemical characterizations of pesticides (amitrole and diuron) and 2-mercaptoethanol (2-ME). The formation of conjugates was confirmed through the use of the following analytical techniques: UV-vis, FTIR, Raman and XRD spectroscopies, atomic force and transmission electron microscopies and voltammetry. Chemically linking SWCNT to MPcs created platforms that offered efficient transfer of electrons and this was confirmed through electrochemical impedance studies (EIS) and voltammetry as shown by lower ΔEp values observed in conjugates. Carboxy carrying MPcs have very poor electron transfer kinetics (both tetrasubstituted and low symmetry), but the presence of SWCNTs activates their catalysis. All electrochemical studies were done at pH 4. Cyclic voltammetry, rotating disk linear sweep voltammetry, chronoamperometry and EIS were used in the electrochemical characterization of 2-ME and the pesticides on poly-Ni(OH)TAPc and MPc-SWCNT modified glassy carbon electrodes (GCEs). High Tafel slopes were observed for the pesticides relative to 2-ME, an indication of the passivating nature of their oxidation products. However, conjugates showed very high resistances to passivation and were easily regenerated by shaking in methanol. Improved catalysis of the conjugates is also indicated by the high catalytic rate constants for the analytes, observed on these electrodes. Conjugates of low symmetry MPcs with SWCNTs gave the highest catalytic rate constants, confirming better catalysis on these electrode surfaces. The nature of SWCNT functionalization also affected catalysis, with amine functionalized SWCNTs inducing better catalytic properties into the MPcs than carboxylic acid terminated CNTs. The presence of amine functionalized SWCNTs activates the catalysis of non-catalytic carboxy-carrying MPcs and this is more pronounced in conjugates of tetrasubstituted MPcs relative to those of low symmetry Pcs. Ethylene amine (EA) functionalized SWCNTs reduced redox overpotentials of the MPcs more than the phenyl-amine (PA) functionalized counterparts. Poly-NiTAPc was successfully converted to poly-Ni(OH)TAPc through cyclisation in pH 4 buffer and showed very good catalytic properties towards diuron, relative to the former.
- Full Text:
- Date Issued: 2011
- Authors: Mugadza, Tawanda
- Date: 2011 , 2011-03-30
- Subjects: Phthalocyanines Pesticides Nanotubes Electrocatalysis Electrochemistry Transmission electron microscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4419 , http://hdl.handle.net/10962/d1006855
- Description: Metallophthalocyanine-single walled carbon nanotube conjugates were successfully synthesized and applied in the electrochemical characterizations of pesticides (amitrole and diuron) and 2-mercaptoethanol (2-ME). The formation of conjugates was confirmed through the use of the following analytical techniques: UV-vis, FTIR, Raman and XRD spectroscopies, atomic force and transmission electron microscopies and voltammetry. Chemically linking SWCNT to MPcs created platforms that offered efficient transfer of electrons and this was confirmed through electrochemical impedance studies (EIS) and voltammetry as shown by lower ΔEp values observed in conjugates. Carboxy carrying MPcs have very poor electron transfer kinetics (both tetrasubstituted and low symmetry), but the presence of SWCNTs activates their catalysis. All electrochemical studies were done at pH 4. Cyclic voltammetry, rotating disk linear sweep voltammetry, chronoamperometry and EIS were used in the electrochemical characterization of 2-ME and the pesticides on poly-Ni(OH)TAPc and MPc-SWCNT modified glassy carbon electrodes (GCEs). High Tafel slopes were observed for the pesticides relative to 2-ME, an indication of the passivating nature of their oxidation products. However, conjugates showed very high resistances to passivation and were easily regenerated by shaking in methanol. Improved catalysis of the conjugates is also indicated by the high catalytic rate constants for the analytes, observed on these electrodes. Conjugates of low symmetry MPcs with SWCNTs gave the highest catalytic rate constants, confirming better catalysis on these electrode surfaces. The nature of SWCNT functionalization also affected catalysis, with amine functionalized SWCNTs inducing better catalytic properties into the MPcs than carboxylic acid terminated CNTs. The presence of amine functionalized SWCNTs activates the catalysis of non-catalytic carboxy-carrying MPcs and this is more pronounced in conjugates of tetrasubstituted MPcs relative to those of low symmetry Pcs. Ethylene amine (EA) functionalized SWCNTs reduced redox overpotentials of the MPcs more than the phenyl-amine (PA) functionalized counterparts. Poly-NiTAPc was successfully converted to poly-Ni(OH)TAPc through cyclisation in pH 4 buffer and showed very good catalytic properties towards diuron, relative to the former.
- Full Text:
- Date Issued: 2011
Monetary policy transmission in South Africa: the prime rate-demand for credit phase
- Authors: Lehobo, Limakatso
- Date: 2006
- Subjects: South African Reserve Bank , Monetary policy -- South Africa , Banks and banking -- South Africa , Bank loans -- South Africa , Financial institutions -- South Africa , Finance -- South Africa
- Language: English
- Type: Thesis , Masters , MCom
- Identifier: vital:1128 , http://hdl.handle.net/10962/d1020850
- Description: A voluminous literature attempts to explain the various channels of the monetary policy transmission mechanism through which central banks ultimately achieve price stability. However, most research focuses on interest rate pass-through and the demand for money phase, while there is limited research on the demand for credit. This study endeavours to contribute to the understanding of this neglected phase of monetary policy transmission by exploring the response of the real demand for bank credit by the private sector to changes in the real prime rate from 1990:1 to 2004:4 in South Africa. Firstly, the behaviour of the real prime rate in relation to the repo rate is explored using graphical analysis. The study observes that an increase in the repo rate causes an increase in the real prime rate, such that there is always a margin of three or four percentage points between the two rates. Secondly, using secondary data, the Johansen methodology is used to determine the relationship between the demand for bank credit and its determinants (GDP, inflation, real prime rate and real yield on government bonds). Two co-integrating relationships are found. The Gaussian errors from one co-integrating vector are used to model the Vector Error Correction Model, which provides the short-run dynamics and the long-run results, through the use of Eviews 5 software. The results of the study show that while all other variables are negatively related to the demand for bank credit in the long-run, GDP has a positive influence. In the short-run, yield on government bonds and inflation coefficients depict a positive association, while the coefficients of real prime rate and GDP are negative. The error correction coefficient is -0.32, which implies that a 32% adjustment to equilibrium happens in the demand for bank credit in a quarter and that the complete adjustment takes about three quarters to complete. Thirdly, the generalised impulse responses results indicate that the impact on the real prime rate affects the demand for bank credit from the first quarter. The study concludes that the real prime rate has a negative impact on the demand for credit both in the short-run and long-run.
- Full Text:
- Date Issued: 2006
- Authors: Lehobo, Limakatso
- Date: 2006
- Subjects: South African Reserve Bank , Monetary policy -- South Africa , Banks and banking -- South Africa , Bank loans -- South Africa , Financial institutions -- South Africa , Finance -- South Africa
- Language: English
- Type: Thesis , Masters , MCom
- Identifier: vital:1128 , http://hdl.handle.net/10962/d1020850
- Description: A voluminous literature attempts to explain the various channels of the monetary policy transmission mechanism through which central banks ultimately achieve price stability. However, most research focuses on interest rate pass-through and the demand for money phase, while there is limited research on the demand for credit. This study endeavours to contribute to the understanding of this neglected phase of monetary policy transmission by exploring the response of the real demand for bank credit by the private sector to changes in the real prime rate from 1990:1 to 2004:4 in South Africa. Firstly, the behaviour of the real prime rate in relation to the repo rate is explored using graphical analysis. The study observes that an increase in the repo rate causes an increase in the real prime rate, such that there is always a margin of three or four percentage points between the two rates. Secondly, using secondary data, the Johansen methodology is used to determine the relationship between the demand for bank credit and its determinants (GDP, inflation, real prime rate and real yield on government bonds). Two co-integrating relationships are found. The Gaussian errors from one co-integrating vector are used to model the Vector Error Correction Model, which provides the short-run dynamics and the long-run results, through the use of Eviews 5 software. The results of the study show that while all other variables are negatively related to the demand for bank credit in the long-run, GDP has a positive influence. In the short-run, yield on government bonds and inflation coefficients depict a positive association, while the coefficients of real prime rate and GDP are negative. The error correction coefficient is -0.32, which implies that a 32% adjustment to equilibrium happens in the demand for bank credit in a quarter and that the complete adjustment takes about three quarters to complete. Thirdly, the generalised impulse responses results indicate that the impact on the real prime rate affects the demand for bank credit from the first quarter. The study concludes that the real prime rate has a negative impact on the demand for credit both in the short-run and long-run.
- Full Text:
- Date Issued: 2006
Synthesis and characterisation of oxorhenium(V) and tricarbonylrhenium(I) complexes with biologically active N, O and N, S-Donor ligands
- Authors: Mukiza, Janvier
- Date: 2013
- Subjects: Rhenium , Rhenium compounds , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10437 , http://hdl.handle.net/10948/d1020769
- Description: This study investigated the synthesis of rhenium(I) and rhenium(V) complexes with a variety of multidentate NS, NSO, NO and SO-donor ligands. It also investigated the synthesis of dinuclear dihalogeno- and trihalogeno-bridged rhenium(I) complexes based on the fac-[Re(CO)3]+ core. The reactions of hydrated folic acid with [Re(CO)5X] (X = Cl, Br) were studied, and the complexes [Re(CO)3(H2O)3]+[Re2(μ-X)3CO)6]−.5H2O [X= Br (1), Cl(2)] were isolated. The reaction of orotic acid potassium salt [Re(CO)5Br] was performed, and the complex [Re2(μ-Br)2(CO)8] was isolated. The reaction of bis(piperidin-1- yl)methanone with [Re(CO)5Cl] followed by recrystallisation of the resulting precipitate in dichloromethane/acetontrile resulted in the complex [Re2(μ- Cl)2(CO)6(MeCN)2]. The X-ray crystal structures show that all these complexes display a distorted octahedral geometry around the central rhenium atoms. The reactions of aroylhydrazone-based ligands such as 3-((pyridin- 2yl)methyleneamino)-2,3-dihydro-2-pyridin-2yl)quinazolin-4-(1H)-one (Hppq) and N-(di(pyridin-2-yl)methylene)benzohydrazide (Hdpmb) with [Re(CO)5Cl] were studied and led to the formation of the complexes [Re(CO)3Cl(Hdpmb)] and [Re(CO)3Cl(Hppq)]. The Hdpmb and Hppq coordinated to the fac-[Re(CO)3]+ core as neutral bidentate chalates via the pyridinic nitrogens (for Hdpmb) and via imino and pyridinic nitrogens for Hppq. The X-ray crystal structures show that the geometry around the rhenium in both complexes is a distorted octahedral. The treatment of the dithizone (H2dz) ligand with rhenium(V) precursors containing a triphenylphosphine group (PPh3) led to the decomposition of dithizone. The decomposition product reacted with the triphenylphosphine group and generated a new ligand triphenylphosphazeno-N-phenylmethanethiohydrazide (H2L). The reaction of trans-[ReOX3(PPh3)2] (X = Cl, Br) with dithizone (H2dz) led to the complex [ReO(dz)2][ReO(HL)2]. The reaction of trans-[ReOI2(OEt)(PPh3)2] with H2dz led to the same product. The reaction of cis-[ReO2I(PPh3)2] with H2dz in methanol led to [ReO(dz)2][ReO(HL)2](MeOH)2 in which methanol bonded to HLvia hydrogen bonds. The H2dz was doubly deprotonated and coordinated to the [ReO]3+ moiety via a thiolate sulfur and deprotonated hydrazinic nitrogen to yield [ReO(dz)2]−, while the H2L was singly deprotonated and coordinated to [ReO]3+ moiety via the neutral sulfur atom and deprotonated hydrazinic nitrogen to yield [ReO(HL)2]+. The X-ray crystal structure show that in both [ReO(HL)2]+ and [ReO(dz)2]−, the rhenium atoms are five-coordinated and adopt a distorted squarebased pyramidal geometry. The reaction of thiosemicarbazones such as salcylidene-4- phenylthiosemicarbazide (H3salpt) with cis-[ReO2I(PPh3)2] was investigated and led to the complex [ReO(Hsalpt)(H2salpt)]. The X-ray study reveals that Hsalpt is present as a tridentate chelate coordinating via the thiolate sulfur, imino nitrogen and phenolic oxygen, while H2salpt coordinates as a bidentate chelate via the thiolate sulfur and imino nitrogen atoms. The geometry around rhenium is distorted octahedral. The coordination mode of the benzoylthiourea derivatives 4-tert-butyl-N- (diphenylcarbamothioyl)benzamide (Htpb) and N-(diethylcarbamothioyl)benzamide (Heb) to the [Re2O3]4+ and fac-[Re(CO)3]+ cores were investigated. The reaction of [Re(CO)5Cl] in presence of sodium acetate with Htpb led to the dimeric complex [Re(CO)3(tpb)]2 in which the tpb coordinated to the fac-[Re(CO)3]+ core via the ketonic oxygen and bridging thiolate sulfur. The same reaction with Heb led to the monomeric complex [Re(CO)3(eb)(Heb)], in which the eb coordinates to the fac-[Re(CO)3]+core via thiolate sulfur and ketonic oxygen with Heb binding via the neutral sulfur atom. The reaction of Heb with cis-[ReO2I(PPh3)2] at room temperature with excess of sodium acetate led to the dimeric complex (μ-O)[ReO(eb)2]2 in which Heb is present as a monoanionic (deprotonated) bidentate with coordination through the thiolate sulfur and ketonic oxygen.
- Full Text:
- Date Issued: 2013
- Authors: Mukiza, Janvier
- Date: 2013
- Subjects: Rhenium , Rhenium compounds , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10437 , http://hdl.handle.net/10948/d1020769
- Description: This study investigated the synthesis of rhenium(I) and rhenium(V) complexes with a variety of multidentate NS, NSO, NO and SO-donor ligands. It also investigated the synthesis of dinuclear dihalogeno- and trihalogeno-bridged rhenium(I) complexes based on the fac-[Re(CO)3]+ core. The reactions of hydrated folic acid with [Re(CO)5X] (X = Cl, Br) were studied, and the complexes [Re(CO)3(H2O)3]+[Re2(μ-X)3CO)6]−.5H2O [X= Br (1), Cl(2)] were isolated. The reaction of orotic acid potassium salt [Re(CO)5Br] was performed, and the complex [Re2(μ-Br)2(CO)8] was isolated. The reaction of bis(piperidin-1- yl)methanone with [Re(CO)5Cl] followed by recrystallisation of the resulting precipitate in dichloromethane/acetontrile resulted in the complex [Re2(μ- Cl)2(CO)6(MeCN)2]. The X-ray crystal structures show that all these complexes display a distorted octahedral geometry around the central rhenium atoms. The reactions of aroylhydrazone-based ligands such as 3-((pyridin- 2yl)methyleneamino)-2,3-dihydro-2-pyridin-2yl)quinazolin-4-(1H)-one (Hppq) and N-(di(pyridin-2-yl)methylene)benzohydrazide (Hdpmb) with [Re(CO)5Cl] were studied and led to the formation of the complexes [Re(CO)3Cl(Hdpmb)] and [Re(CO)3Cl(Hppq)]. The Hdpmb and Hppq coordinated to the fac-[Re(CO)3]+ core as neutral bidentate chalates via the pyridinic nitrogens (for Hdpmb) and via imino and pyridinic nitrogens for Hppq. The X-ray crystal structures show that the geometry around the rhenium in both complexes is a distorted octahedral. The treatment of the dithizone (H2dz) ligand with rhenium(V) precursors containing a triphenylphosphine group (PPh3) led to the decomposition of dithizone. The decomposition product reacted with the triphenylphosphine group and generated a new ligand triphenylphosphazeno-N-phenylmethanethiohydrazide (H2L). The reaction of trans-[ReOX3(PPh3)2] (X = Cl, Br) with dithizone (H2dz) led to the complex [ReO(dz)2][ReO(HL)2]. The reaction of trans-[ReOI2(OEt)(PPh3)2] with H2dz led to the same product. The reaction of cis-[ReO2I(PPh3)2] with H2dz in methanol led to [ReO(dz)2][ReO(HL)2](MeOH)2 in which methanol bonded to HLvia hydrogen bonds. The H2dz was doubly deprotonated and coordinated to the [ReO]3+ moiety via a thiolate sulfur and deprotonated hydrazinic nitrogen to yield [ReO(dz)2]−, while the H2L was singly deprotonated and coordinated to [ReO]3+ moiety via the neutral sulfur atom and deprotonated hydrazinic nitrogen to yield [ReO(HL)2]+. The X-ray crystal structure show that in both [ReO(HL)2]+ and [ReO(dz)2]−, the rhenium atoms are five-coordinated and adopt a distorted squarebased pyramidal geometry. The reaction of thiosemicarbazones such as salcylidene-4- phenylthiosemicarbazide (H3salpt) with cis-[ReO2I(PPh3)2] was investigated and led to the complex [ReO(Hsalpt)(H2salpt)]. The X-ray study reveals that Hsalpt is present as a tridentate chelate coordinating via the thiolate sulfur, imino nitrogen and phenolic oxygen, while H2salpt coordinates as a bidentate chelate via the thiolate sulfur and imino nitrogen atoms. The geometry around rhenium is distorted octahedral. The coordination mode of the benzoylthiourea derivatives 4-tert-butyl-N- (diphenylcarbamothioyl)benzamide (Htpb) and N-(diethylcarbamothioyl)benzamide (Heb) to the [Re2O3]4+ and fac-[Re(CO)3]+ cores were investigated. The reaction of [Re(CO)5Cl] in presence of sodium acetate with Htpb led to the dimeric complex [Re(CO)3(tpb)]2 in which the tpb coordinated to the fac-[Re(CO)3]+ core via the ketonic oxygen and bridging thiolate sulfur. The same reaction with Heb led to the monomeric complex [Re(CO)3(eb)(Heb)], in which the eb coordinates to the fac-[Re(CO)3]+core via thiolate sulfur and ketonic oxygen with Heb binding via the neutral sulfur atom. The reaction of Heb with cis-[ReO2I(PPh3)2] at room temperature with excess of sodium acetate led to the dimeric complex (μ-O)[ReO(eb)2]2 in which Heb is present as a monoanionic (deprotonated) bidentate with coordination through the thiolate sulfur and ketonic oxygen.
- Full Text:
- Date Issued: 2013
Trends of parent involvement in the intermediate phase in Jan Nomjana J.S.S at Kotana administration area of Ngqamakwe
- Authors: Gwalisa, Nondumiso Enid
- Date: 2013
- Subjects: Education -- Parent participation -- South Africa -- Eastern Cape , Home and school -- South Africa -- Eastern Cape , Parent-teacher relationships -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:9223 , http://hdl.handle.net/10948/d1020951
- Description: This research sought to better understand and explain the factors that account for the non-involvement of parents in their children’s school affairs. It also sought to recommend to the Department of Education developmental strategies that can be utilised towards ensuring the participation of parents by equipping them with knowledge and skills that can help them to become more involved in the success of their children in schools. This research employed a case study design to collect data from parents and teachers using qualitative methods. The qualitative approach was considered appropriate because it affords both exploration and explanation of parents’ non-involvement in the Kotana administrative Area in which three schools were selected by the researcher. Interviews with a total of nine participants constituted by both parents and teachers were conducted. These tape recorded interviews were then transcribed and interpreted by the researcher. Emerging themes were then extracted and presented as explanatory findings on the issue of the non-involvement of parents in their children’s schooling matters. The study found that the level of education; fear of victimisation; language barrier; poor communication of information; lack of personal time; lack of confidence on the part of parents; cultural expectations; transport problems; misbehaviour by teenagers; HIV and AIDS; and the new curriculum accounts for parental non-involvement, and uncovered reasons for non-participation by parents in the affairs of their children at school.
- Full Text:
- Date Issued: 2013
- Authors: Gwalisa, Nondumiso Enid
- Date: 2013
- Subjects: Education -- Parent participation -- South Africa -- Eastern Cape , Home and school -- South Africa -- Eastern Cape , Parent-teacher relationships -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:9223 , http://hdl.handle.net/10948/d1020951
- Description: This research sought to better understand and explain the factors that account for the non-involvement of parents in their children’s school affairs. It also sought to recommend to the Department of Education developmental strategies that can be utilised towards ensuring the participation of parents by equipping them with knowledge and skills that can help them to become more involved in the success of their children in schools. This research employed a case study design to collect data from parents and teachers using qualitative methods. The qualitative approach was considered appropriate because it affords both exploration and explanation of parents’ non-involvement in the Kotana administrative Area in which three schools were selected by the researcher. Interviews with a total of nine participants constituted by both parents and teachers were conducted. These tape recorded interviews were then transcribed and interpreted by the researcher. Emerging themes were then extracted and presented as explanatory findings on the issue of the non-involvement of parents in their children’s schooling matters. The study found that the level of education; fear of victimisation; language barrier; poor communication of information; lack of personal time; lack of confidence on the part of parents; cultural expectations; transport problems; misbehaviour by teenagers; HIV and AIDS; and the new curriculum accounts for parental non-involvement, and uncovered reasons for non-participation by parents in the affairs of their children at school.
- Full Text:
- Date Issued: 2013
Potential for human exposure to Beta-N-methylamino-L-alanine in a freshwater system
- Authors: Scott, Laura Louise
- Date: 2014
- Subjects: Water quality biological assessment , Cyanobacteria , Neurotoxic agents
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/5159 , vital:20816
- Description: β-N-methylamino-L-alanine (BMAA) is a non-proteinogenic amino acid associated with human neurodegenerative diseases. The content of BMAA in cyanobacteria is modulated by nitrogen in laboratory cultures. In order to evaluate the potential for human exposure, the nitrogen modulation of BMAA content needed verification in a natural environment. In accordance with laboratory culture studies, data presented in this study show that combined nitrogen was the most significant modulator of both cellular microcystin (MC) and BMAA content in phytoplankton in an environmental cyanobacterial bloom. While BMAA is produced upon nitrogen deprivation, MC is only produced at a specific nitrogen threshold where the rate of increase of nitrogen in the cell exceeds the carbon fixation rate. As BMAA and MC were detected in phytoplankton sourced from the Hartbeespoort Dam reservoir, the transfer of these cyanotoxins to organisms of higher trophic levels was investigated. Both BMAA and MC were detected at high concentrations in the liver and muscle tissue of fish sourced from the Hartbeespoort Dam reservoir indicating that consumption of fish from this reservoir constitutes a serious risk of exposure to cyanotoxins. In addition to the dietary exposure route to BMAA, two recent studies reported a correlation between Amyotrophic Lateral Sclerosis (ALS) incidence and the potential for aerosol exposure to cyanobacteria. With the absence of any evidence of the systemic distribution of BMAA following inhalation, an evaluation of the potential exposure risk associated with living in close proximity to this reservoir was deemed premature. A laboratory experiment investigating the effect and systemic fate of inhaled aerosolised BMAA was therefore conducted in order to determine the feasibility of inhalation as a potential BMAA exposure route. Data from the rat inhalation exposure study, however, showed that in rats BMAA inhalation may not constitute a significant mechanism of toxicity at environmental BMAA levels.
- Full Text:
- Date Issued: 2014
- Authors: Scott, Laura Louise
- Date: 2014
- Subjects: Water quality biological assessment , Cyanobacteria , Neurotoxic agents
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/5159 , vital:20816
- Description: β-N-methylamino-L-alanine (BMAA) is a non-proteinogenic amino acid associated with human neurodegenerative diseases. The content of BMAA in cyanobacteria is modulated by nitrogen in laboratory cultures. In order to evaluate the potential for human exposure, the nitrogen modulation of BMAA content needed verification in a natural environment. In accordance with laboratory culture studies, data presented in this study show that combined nitrogen was the most significant modulator of both cellular microcystin (MC) and BMAA content in phytoplankton in an environmental cyanobacterial bloom. While BMAA is produced upon nitrogen deprivation, MC is only produced at a specific nitrogen threshold where the rate of increase of nitrogen in the cell exceeds the carbon fixation rate. As BMAA and MC were detected in phytoplankton sourced from the Hartbeespoort Dam reservoir, the transfer of these cyanotoxins to organisms of higher trophic levels was investigated. Both BMAA and MC were detected at high concentrations in the liver and muscle tissue of fish sourced from the Hartbeespoort Dam reservoir indicating that consumption of fish from this reservoir constitutes a serious risk of exposure to cyanotoxins. In addition to the dietary exposure route to BMAA, two recent studies reported a correlation between Amyotrophic Lateral Sclerosis (ALS) incidence and the potential for aerosol exposure to cyanobacteria. With the absence of any evidence of the systemic distribution of BMAA following inhalation, an evaluation of the potential exposure risk associated with living in close proximity to this reservoir was deemed premature. A laboratory experiment investigating the effect and systemic fate of inhaled aerosolised BMAA was therefore conducted in order to determine the feasibility of inhalation as a potential BMAA exposure route. Data from the rat inhalation exposure study, however, showed that in rats BMAA inhalation may not constitute a significant mechanism of toxicity at environmental BMAA levels.
- Full Text:
- Date Issued: 2014
Complexes of the ReO³⁺/Re(CO)₃cores with multidentate N,O-Donor chelates
- Authors: Potgieter, Kim Carey
- Date: 2009
- Subjects: Rhenium , Schiff bases
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10387 , http://hdl.handle.net/10948/1225 , Rhenium , Schiff bases
- Description: This study investigates the coordination modes of multidentate N,O-donor ligands toward the [ReVO]3+ and fac-[ReI(CO)3]+ cores. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with 4-aminoantipyrine (H2pap) were studied, and the complexes cis-[ReX2(pap)(H2pap)(PPh3)](ReO4) were isolated. The X-ray crystal structures show that both complexes display a distorted octahedral geometry around the central rhenium atom, and are mirror images of each other. The ligand pap is coordinated monodentately through the doubly deprotonated amino nitrogen as an imide, and H2pap acts as a neutral bidentate chelate, with coordination through the neutral amino nitrogen and the ketonic oxygen. The attempted synthesis of the potentially hexadentate Schiff base ligand 1,2-bis(2-{(Z)- [(2-hydroxyphenyl)imido]methyl}phenoxy)benzene from the condensation reaction of 2- (2-((2-aminophenoxy)methyl)benzyloxy)benzenamine and salicylaldehyde produced the zwitterion derivative (H2ono) of 2-{(Z)-[2-(hydroxyphenyl)imino]methyl}phenol. The tridentate Schiff bases (Z)-2-(2-aminobenzylideneamino)phenol (H3onn) and (Z)-2-(2- (methylthio)benzylideneamino)phenol (Hons) were prepared in a similar manner. The reaction of H2ono with trans-[ReOBr3(PPh3)2] surprisingly led to the isolation of the rhenium(III) complex [ReBr(PPh3)2(ono)], in which ono acts as a dianionic tridentate ligand. The reaction of H3onn with trans-[ReOBr3(PPh3)2] produced the imidorhenium(V) complex salt [ReBr(PPh3)2(onn)]Br, in which onn is coordinated as a trianionic tridentate imidoiminophenolate. The reaction of Hons with [Re(CO)5Br] led to the further decomposition of the Hons ligand, and the rhenium(I) product fac- [Re(CO)3(ons)(Hno)] (Hno = 2-aminophenol) was isolated, with ons coordinated as a monoanionic bidentate chelate (with a free SCH3 group), and Hno present as a neutral monodentate ligand with coordination through the amino nitrogen atom. Abstract Nelson Mandela Metropolitan University vi The reactions of the potentially hexadentate ligand N,N’-{ethane-1,2- diylbis[nitrilomethylidenebenzene-1,2-diyl]}bis(2-aminobenzeneimine) (H2ted) with rhenium(V) starting materials resulted in the decomposition of the H2ted molecule to give different coordinated multidentate ligands coordinated to the rhenium(V) centers. In the reaction of H2ted with trans-[ReOBr3(PPh3)2] in ethanol, the highly unusual ‘3+3’ complex cation [Re(tnn)(Htnn)]Br2 was isolated, in which tnn is coordinated as a tridentate imido-imino-amine, and Htnn is present as a tridentate monoanionic amidoimino- amine chelate (H2tnn = N-(2-aminophenylmethylidene)ethane-1,2-diamine). With trans-[ReO2(py)4]Cl as starting material, the neutral complex [ReO(dne)] was found, in which the tetradentate chelate dne acts as a triamido-imine. The reaction of cis- [ReO2I(PPh3)2] with H2ted led to the formation of the monocationic complex salt [ReO(ane)]PF6, with ane acting as a tetradentate dianionic diamidodiimine (H2ane = N,N’-bis[(2-aminophenyl)methylidene] ethane-1,2-diamine). The seven-coordinate rhenium(III) complex cation [Re(dhp)(PPh3)2]+ (H2dhp = 2,6-bis(2- hydroxyphenyliminomethyl)pyridine) was isolated as the iodide salt from the reaction of cis-[ReO2I(PPh3)2] with H2dhp in ethanol and as the perrhenate salt from the reaction of trans-[ReOBr3(PPh3)2] with H2dhp in methanol. Both products result from a disproportionation reaction with perrhenate also being produced in the process. The complex fac-[Re(CO)3(H2dhp)Br] was prepared from [Re(CO)5Br] and H2dhp in toluene, where the H2dhp ligand acts as a neutral bidentate NN-donor chelate. The metal is coordinated to three carbonyl donors in a facial orientation, to a neutral imino nitrogen, a pyridinic nitrogen and a bromide.
- Full Text:
- Date Issued: 2009
- Authors: Potgieter, Kim Carey
- Date: 2009
- Subjects: Rhenium , Schiff bases
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10387 , http://hdl.handle.net/10948/1225 , Rhenium , Schiff bases
- Description: This study investigates the coordination modes of multidentate N,O-donor ligands toward the [ReVO]3+ and fac-[ReI(CO)3]+ cores. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with 4-aminoantipyrine (H2pap) were studied, and the complexes cis-[ReX2(pap)(H2pap)(PPh3)](ReO4) were isolated. The X-ray crystal structures show that both complexes display a distorted octahedral geometry around the central rhenium atom, and are mirror images of each other. The ligand pap is coordinated monodentately through the doubly deprotonated amino nitrogen as an imide, and H2pap acts as a neutral bidentate chelate, with coordination through the neutral amino nitrogen and the ketonic oxygen. The attempted synthesis of the potentially hexadentate Schiff base ligand 1,2-bis(2-{(Z)- [(2-hydroxyphenyl)imido]methyl}phenoxy)benzene from the condensation reaction of 2- (2-((2-aminophenoxy)methyl)benzyloxy)benzenamine and salicylaldehyde produced the zwitterion derivative (H2ono) of 2-{(Z)-[2-(hydroxyphenyl)imino]methyl}phenol. The tridentate Schiff bases (Z)-2-(2-aminobenzylideneamino)phenol (H3onn) and (Z)-2-(2- (methylthio)benzylideneamino)phenol (Hons) were prepared in a similar manner. The reaction of H2ono with trans-[ReOBr3(PPh3)2] surprisingly led to the isolation of the rhenium(III) complex [ReBr(PPh3)2(ono)], in which ono acts as a dianionic tridentate ligand. The reaction of H3onn with trans-[ReOBr3(PPh3)2] produced the imidorhenium(V) complex salt [ReBr(PPh3)2(onn)]Br, in which onn is coordinated as a trianionic tridentate imidoiminophenolate. The reaction of Hons with [Re(CO)5Br] led to the further decomposition of the Hons ligand, and the rhenium(I) product fac- [Re(CO)3(ons)(Hno)] (Hno = 2-aminophenol) was isolated, with ons coordinated as a monoanionic bidentate chelate (with a free SCH3 group), and Hno present as a neutral monodentate ligand with coordination through the amino nitrogen atom. Abstract Nelson Mandela Metropolitan University vi The reactions of the potentially hexadentate ligand N,N’-{ethane-1,2- diylbis[nitrilomethylidenebenzene-1,2-diyl]}bis(2-aminobenzeneimine) (H2ted) with rhenium(V) starting materials resulted in the decomposition of the H2ted molecule to give different coordinated multidentate ligands coordinated to the rhenium(V) centers. In the reaction of H2ted with trans-[ReOBr3(PPh3)2] in ethanol, the highly unusual ‘3+3’ complex cation [Re(tnn)(Htnn)]Br2 was isolated, in which tnn is coordinated as a tridentate imido-imino-amine, and Htnn is present as a tridentate monoanionic amidoimino- amine chelate (H2tnn = N-(2-aminophenylmethylidene)ethane-1,2-diamine). With trans-[ReO2(py)4]Cl as starting material, the neutral complex [ReO(dne)] was found, in which the tetradentate chelate dne acts as a triamido-imine. The reaction of cis- [ReO2I(PPh3)2] with H2ted led to the formation of the monocationic complex salt [ReO(ane)]PF6, with ane acting as a tetradentate dianionic diamidodiimine (H2ane = N,N’-bis[(2-aminophenyl)methylidene] ethane-1,2-diamine). The seven-coordinate rhenium(III) complex cation [Re(dhp)(PPh3)2]+ (H2dhp = 2,6-bis(2- hydroxyphenyliminomethyl)pyridine) was isolated as the iodide salt from the reaction of cis-[ReO2I(PPh3)2] with H2dhp in ethanol and as the perrhenate salt from the reaction of trans-[ReOBr3(PPh3)2] with H2dhp in methanol. Both products result from a disproportionation reaction with perrhenate also being produced in the process. The complex fac-[Re(CO)3(H2dhp)Br] was prepared from [Re(CO)5Br] and H2dhp in toluene, where the H2dhp ligand acts as a neutral bidentate NN-donor chelate. The metal is coordinated to three carbonyl donors in a facial orientation, to a neutral imino nitrogen, a pyridinic nitrogen and a bromide.
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- Date Issued: 2009