Synthesis, crystal structures and molecular modelling of rare earth complexes with bis(2-pyridylmethyl)amine: aim topological analysis and ligand conformation search
- Authors: Matthews, Cameron
- Date: 2017
- Subjects: Rare earths , Ligands , Complex compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/8230 , vital:26229
- Description: Eight rare earth complexes with bis(2-pyridylmethyl)amine (DPA) were synthesised and recrystallised, under air-sensitive or low moisture conditions. The crystal structures were successfully determined, via SC-XRD, and the asymmetric units of five complexes (1, 3, 5, 6 and 7) were submitted for DFT molecular modelling calculations, which involved geometry optimisation and frequency calculations. The neutral complexes obtained were bis(bis(2-pyridylmethyl)amine)-trichloro-lanthanum(III) [LaCl3(DPA)2] (1), bis(bis(2-pyridylmethyl)amine)-trichloro-cerium(III)) [CeCl3(DPA)2] (2), bis(μ2-chloro)-diaqua-tetrachloro-bis(bis(2-pyridylmethyl)amine)-di-praseodymium(III) [PrCl2(μ-Cl)(DPA)(OH2)]2 (3) and bis(μ2-methoxo)-bis(bis(2-pyridylmethyl)amine)- tetrachloro-di-dysprosium(III) [DyCl2(μ-OCH3)(DPA)]2 (4). The cationic complexes obtained in this study were dichloro-bis(bis(2-pyridylmethyl)amine)- neodymium(III) chloride methanol solvate [NdCl2(DPA)2]Cl·CH3OH (5), dichloro-bis(bis(2- pyridylmethyl)amine)-dysprosium(III) chloride methanol solvate [DyCl2(DPA)2]Cl·CH3OH (6), dichloro-bis(bis(2-pyridylmethyl)amine)-yttrium(III) chloride methanol solvate [YCl2(DPA)2]Cl·CH3OH (7) and dichloro-bis(bis(2-pyridylmethyl)amine)-lutetium(III) chloride methanol solvate [LuCl2(DPA)2]Cl·CH3OH (8). The ‘Quantum theory of atoms in molecules’ approach was used to investigate the electron density topology, primarily in order to investigate the hydrogen and coordination bonds for three of the eight complexes. Two of the neutral complexes contain the ‘early’ rare earth elements lanthanum and praseodymium and one cationic complex contains the ‘late’ lanthanide element dysprosium. Noncovalent interaction analysis was also performed on the aforementioned complexes in order to gain a deeper understanding of the intra-molecular stereo-electronic interactions. Spin density analysis was used to investigate the distribution of unpaired electron density at and around the metal centres of the aforementioned paramagnetic Pr- and Dy-complexes. A ligand conformation search for DPA was undertaken and 32 low energy conformers were identified and their relative energies were determined using two DFT functionals, namely M06 and M06-2X.
- Full Text:
- Date Issued: 2017
- Authors: Matthews, Cameron
- Date: 2017
- Subjects: Rare earths , Ligands , Complex compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/8230 , vital:26229
- Description: Eight rare earth complexes with bis(2-pyridylmethyl)amine (DPA) were synthesised and recrystallised, under air-sensitive or low moisture conditions. The crystal structures were successfully determined, via SC-XRD, and the asymmetric units of five complexes (1, 3, 5, 6 and 7) were submitted for DFT molecular modelling calculations, which involved geometry optimisation and frequency calculations. The neutral complexes obtained were bis(bis(2-pyridylmethyl)amine)-trichloro-lanthanum(III) [LaCl3(DPA)2] (1), bis(bis(2-pyridylmethyl)amine)-trichloro-cerium(III)) [CeCl3(DPA)2] (2), bis(μ2-chloro)-diaqua-tetrachloro-bis(bis(2-pyridylmethyl)amine)-di-praseodymium(III) [PrCl2(μ-Cl)(DPA)(OH2)]2 (3) and bis(μ2-methoxo)-bis(bis(2-pyridylmethyl)amine)- tetrachloro-di-dysprosium(III) [DyCl2(μ-OCH3)(DPA)]2 (4). The cationic complexes obtained in this study were dichloro-bis(bis(2-pyridylmethyl)amine)- neodymium(III) chloride methanol solvate [NdCl2(DPA)2]Cl·CH3OH (5), dichloro-bis(bis(2- pyridylmethyl)amine)-dysprosium(III) chloride methanol solvate [DyCl2(DPA)2]Cl·CH3OH (6), dichloro-bis(bis(2-pyridylmethyl)amine)-yttrium(III) chloride methanol solvate [YCl2(DPA)2]Cl·CH3OH (7) and dichloro-bis(bis(2-pyridylmethyl)amine)-lutetium(III) chloride methanol solvate [LuCl2(DPA)2]Cl·CH3OH (8). The ‘Quantum theory of atoms in molecules’ approach was used to investigate the electron density topology, primarily in order to investigate the hydrogen and coordination bonds for three of the eight complexes. Two of the neutral complexes contain the ‘early’ rare earth elements lanthanum and praseodymium and one cationic complex contains the ‘late’ lanthanide element dysprosium. Noncovalent interaction analysis was also performed on the aforementioned complexes in order to gain a deeper understanding of the intra-molecular stereo-electronic interactions. Spin density analysis was used to investigate the distribution of unpaired electron density at and around the metal centres of the aforementioned paramagnetic Pr- and Dy-complexes. A ligand conformation search for DPA was undertaken and 32 low energy conformers were identified and their relative energies were determined using two DFT functionals, namely M06 and M06-2X.
- Full Text:
- Date Issued: 2017
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
The design and synthesis of multidentate N-heterocyclic carbenes as metathesis catalyst ligands
- Authors: Truscott, Byron John
- Date: 2011
- Subjects: Carbenes (Methylene compounds) , Heterocyclic compounds , Ligands , Ligands -- Design , Metathesis (Chemistry) , Catalysis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4304 , http://hdl.handle.net/10962/d1004962 , Carbenes (Methylene compounds) , Heterocyclic compounds , Ligands , Ligands -- Design , Metathesis (Chemistry) , Catalysis
- Description: This study has focused on the design and preparation of bi– and tridentate N–Heterocyclic Carbene (NHC) ligands in order to investigate the effect of a multidentate approach to the formation, stability and catalytic activity of coordination complexes. Chapters 1 – 3 provide background information of relevant catalysis, carbene and coordination chemistry, followed by previous work performed within our research group. In Chapter 4 attention is given to the synthetic aspects of the research conducted, comprising two distinct approaches to the preparation of unsymmetrical saturated and unsaturated NHCs. Firstly, an investigation of the saturated NHC ligands yielded three novel, unsymmetrical pro–ligands, viz., two halopropyl imidazolinium salts and a bidentate hydroxypropyl imidazolinium salt. Secondly, eight imidazolium salts have been generated, including a hydroxypropyl analogue and novel decyl and tridentate malonyl derivatives. These compounds were prepared using microwave–assisted methodology for the alkylation of N– mesitylimidazole – an approach that drastically reduced reaction times (from 8 hours – 7 days to ca. 0.5 – 2 hours) and facilitated isolation of the imidazolium salts. Many of the compounds prepared in this study are novel and were fully characterized using HRMS and 1– and 2–D NMR analysis. Coordination studies using a selection of the prepared pro–ligands afforded an alkoxy–NHC silver derivative and four novel Ru–complexes, viz., Grubbs II–type Ru–complexes containing:– chloropropyl imidazolinylidene; propenyl imidazolylidene; and bidentate alkoxypropyl imidazolylidene ligands. Furthermore, a well–defined benzyl mesitylimidazolylidene Ru–complex has been isolated, which exhibited good stability in air. DFT–level geometry–optimization studies, using the Accelrys DMol3 package have given valuable insights into the likely geometries of the prepared and putative catalysts.
- Full Text:
- Date Issued: 2011
- Authors: Truscott, Byron John
- Date: 2011
- Subjects: Carbenes (Methylene compounds) , Heterocyclic compounds , Ligands , Ligands -- Design , Metathesis (Chemistry) , Catalysis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4304 , http://hdl.handle.net/10962/d1004962 , Carbenes (Methylene compounds) , Heterocyclic compounds , Ligands , Ligands -- Design , Metathesis (Chemistry) , Catalysis
- Description: This study has focused on the design and preparation of bi– and tridentate N–Heterocyclic Carbene (NHC) ligands in order to investigate the effect of a multidentate approach to the formation, stability and catalytic activity of coordination complexes. Chapters 1 – 3 provide background information of relevant catalysis, carbene and coordination chemistry, followed by previous work performed within our research group. In Chapter 4 attention is given to the synthetic aspects of the research conducted, comprising two distinct approaches to the preparation of unsymmetrical saturated and unsaturated NHCs. Firstly, an investigation of the saturated NHC ligands yielded three novel, unsymmetrical pro–ligands, viz., two halopropyl imidazolinium salts and a bidentate hydroxypropyl imidazolinium salt. Secondly, eight imidazolium salts have been generated, including a hydroxypropyl analogue and novel decyl and tridentate malonyl derivatives. These compounds were prepared using microwave–assisted methodology for the alkylation of N– mesitylimidazole – an approach that drastically reduced reaction times (from 8 hours – 7 days to ca. 0.5 – 2 hours) and facilitated isolation of the imidazolium salts. Many of the compounds prepared in this study are novel and were fully characterized using HRMS and 1– and 2–D NMR analysis. Coordination studies using a selection of the prepared pro–ligands afforded an alkoxy–NHC silver derivative and four novel Ru–complexes, viz., Grubbs II–type Ru–complexes containing:– chloropropyl imidazolinylidene; propenyl imidazolylidene; and bidentate alkoxypropyl imidazolylidene ligands. Furthermore, a well–defined benzyl mesitylimidazolylidene Ru–complex has been isolated, which exhibited good stability in air. DFT–level geometry–optimization studies, using the Accelrys DMol3 package have given valuable insights into the likely geometries of the prepared and putative catalysts.
- Full Text:
- Date Issued: 2011
The development of amine-based extractants for separation of base metals in a sulfate medium
- Authors: Magwa, Nomampondo Penelope
- Date: 2015
- Subjects: Extraction (Chemistry) , Sulfates , Ligands , Benzimidazoles , Infrared spectroscopy , Nuclear magnetic resonance spectroscopy , Metal ions , Metals
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4559 , http://hdl.handle.net/10962/d1020010
- Description: Tridentate benzimidazole-based ligands, bis((1H-benzimidazol-2-yl)methyl)sulfide (BNSN) and bis((1H-benzimidazol-2-yl)methyl)amine (BNNN), along with dinonylnaphthalene sulfonic acid (DNNSA) as a synergist, were investigated as potential selective extractants for Ni2+ from base metals in a solvent extraction system using 2-octanol/Shellsol 2325 (8:2) as diluent and modifier. However, extraction studies show a lack of pH-metric separation of the later 3d metal ions with bis((1-octylbenzimidazol-2-yl)methyl)sulfide (BONSN) and bis((1- decylbenzimidazol-2-yl)methyl)amine (BDNNN) as extractants, but extractions occurred in the low pH range with an opportunity for back extraction. This investigation suggested that tridentate ligands (at least those of the nature investigated here) are not feasible extractants for separation of base metal ions due to their lack of stereochemical “tailor-making.”
- Full Text:
- Date Issued: 2015
- Authors: Magwa, Nomampondo Penelope
- Date: 2015
- Subjects: Extraction (Chemistry) , Sulfates , Ligands , Benzimidazoles , Infrared spectroscopy , Nuclear magnetic resonance spectroscopy , Metal ions , Metals
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4559 , http://hdl.handle.net/10962/d1020010
- Description: Tridentate benzimidazole-based ligands, bis((1H-benzimidazol-2-yl)methyl)sulfide (BNSN) and bis((1H-benzimidazol-2-yl)methyl)amine (BNNN), along with dinonylnaphthalene sulfonic acid (DNNSA) as a synergist, were investigated as potential selective extractants for Ni2+ from base metals in a solvent extraction system using 2-octanol/Shellsol 2325 (8:2) as diluent and modifier. However, extraction studies show a lack of pH-metric separation of the later 3d metal ions with bis((1-octylbenzimidazol-2-yl)methyl)sulfide (BONSN) and bis((1- decylbenzimidazol-2-yl)methyl)amine (BDNNN) as extractants, but extractions occurred in the low pH range with an opportunity for back extraction. This investigation suggested that tridentate ligands (at least those of the nature investigated here) are not feasible extractants for separation of base metal ions due to their lack of stereochemical “tailor-making.”
- Full Text:
- Date Issued: 2015