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Transition metal complexes of phosphine and mixed phosphathia ligands

Transition metal complexes of phosphine and mixed phosphathia ligands
Transition metal complexes of phosphine and mixed phosphathia ligands

A range of co-ordination complexes have been synthesised and characterised.

The assigned formulae of the tetradentate phosphathia and phospha complexes are: [M(L)Y2 (M = Ni; Pd, Pt; Y = BF4 {Ni}, PF6 {Pd, Pt}), [PtX2(L)](PF6)2 (X =Cl, Br), [RuCl2(L)], [RuCl2(Tetraphos-1)], [CoX(L)]PF6 (X = Cl, Br), [CoX2(L)]Y (X = Cl, Br; Y = Cl/CoCl4, Br/CoBr4), [MCl2(L)]PF6(M = Rh, Ir), [RhCl2(Tetraphos-1)]PF6 and [IrCl2(Tetraphos-1)]PF6 (L = Ph2P(CH2)2S(CH2)2S(CH2)2PPh2, Ph2P(CH2)2S(CH2)3S(CH2)2PPh2). X-ray crystal structures were collected and solved for trans-[Pt{Ph2P(CH2)2S(CH2)3S(CH2)2PPh2}](PF6)2.MeCN, DL-cis-α-[RuCl2{Ph2P(CH2)2S(CH2)2S(CH2)2PPh2}].0.75Et2O, DL-cis-α-[CoCl2{Ph2P(CH2)2S(CH2)3S(CH2)2PPh2}]2[CoCl4].4H2O, DL-cis-α-[RhCl2{Ph2P(CH2)2S(CH2)2S(CH2)2PPh2}]PF6.CH2Cl2.

The two P2S2 ligands and Tetraphos-1 co-ordinate fully to a range of transition metal ions. The favoured geometry of the octahedral complexes is DL-cis-α.

The assigned formulae of the secondary and primary phosphine complexes are: [MX2(L)4] (M = Ru, Os; X = Cl, Br; L = PPhH2, PPh2H), [OsX2(PCy2H)4] (X = Cl, Br), [NiCl2(PCy2H)2], [MCl(PCy2H)3]PF6 (M = Pd, Pt), [Ni{PhHP(CH2)2PPhH}2]Cl2, [M(L)2](PF6)2 (M = Pd, Pt) and [RuCl2(L)2] (L = PhHP(CH2)nPPhH {n = 2, 3}) X-ray crystal structures were collected and solved for trans-{RuCl2(PPhH2)4], trans-[RuBr2(PPhH2)4], trans-[OsCl2(PPh2H)4].CH2Cl2 and trans-[OsBr2(PPh2H)4].Et2O.

The secondary and primary monodentate and secondary bidentate phosphines co-ordinate without deprotonation. The octahedral complexes prefer a trans geometry.

The complexes have been characterised with 31P, 195Pt, 59Co, 103Rh and 1H NMR spectroscopies, X-ray crystallography, IR and UV/Vis spectroscopies, FAB and ES+ mass spectrometries, cyclic voltammetry and elemental microanalysis.

University of Southampton
Forder, Robin James
Forder, Robin James

Forder, Robin James (1996) Transition metal complexes of phosphine and mixed phosphathia ligands. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)

Abstract

A range of co-ordination complexes have been synthesised and characterised.

The assigned formulae of the tetradentate phosphathia and phospha complexes are: [M(L)Y2 (M = Ni; Pd, Pt; Y = BF4 {Ni}, PF6 {Pd, Pt}), [PtX2(L)](PF6)2 (X =Cl, Br), [RuCl2(L)], [RuCl2(Tetraphos-1)], [CoX(L)]PF6 (X = Cl, Br), [CoX2(L)]Y (X = Cl, Br; Y = Cl/CoCl4, Br/CoBr4), [MCl2(L)]PF6(M = Rh, Ir), [RhCl2(Tetraphos-1)]PF6 and [IrCl2(Tetraphos-1)]PF6 (L = Ph2P(CH2)2S(CH2)2S(CH2)2PPh2, Ph2P(CH2)2S(CH2)3S(CH2)2PPh2). X-ray crystal structures were collected and solved for trans-[Pt{Ph2P(CH2)2S(CH2)3S(CH2)2PPh2}](PF6)2.MeCN, DL-cis-α-[RuCl2{Ph2P(CH2)2S(CH2)2S(CH2)2PPh2}].0.75Et2O, DL-cis-α-[CoCl2{Ph2P(CH2)2S(CH2)3S(CH2)2PPh2}]2[CoCl4].4H2O, DL-cis-α-[RhCl2{Ph2P(CH2)2S(CH2)2S(CH2)2PPh2}]PF6.CH2Cl2.

The two P2S2 ligands and Tetraphos-1 co-ordinate fully to a range of transition metal ions. The favoured geometry of the octahedral complexes is DL-cis-α.

The assigned formulae of the secondary and primary phosphine complexes are: [MX2(L)4] (M = Ru, Os; X = Cl, Br; L = PPhH2, PPh2H), [OsX2(PCy2H)4] (X = Cl, Br), [NiCl2(PCy2H)2], [MCl(PCy2H)3]PF6 (M = Pd, Pt), [Ni{PhHP(CH2)2PPhH}2]Cl2, [M(L)2](PF6)2 (M = Pd, Pt) and [RuCl2(L)2] (L = PhHP(CH2)nPPhH {n = 2, 3}) X-ray crystal structures were collected and solved for trans-{RuCl2(PPhH2)4], trans-[RuBr2(PPhH2)4], trans-[OsCl2(PPh2H)4].CH2Cl2 and trans-[OsBr2(PPh2H)4].Et2O.

The secondary and primary monodentate and secondary bidentate phosphines co-ordinate without deprotonation. The octahedral complexes prefer a trans geometry.

The complexes have been characterised with 31P, 195Pt, 59Co, 103Rh and 1H NMR spectroscopies, X-ray crystallography, IR and UV/Vis spectroscopies, FAB and ES+ mass spectrometries, cyclic voltammetry and elemental microanalysis.

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Published date: 1996
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Identifiers

Local EPrints ID: 459825
URI: http://eprints.soton.ac.uk/id/eprint/459825
PURE UUID: 0bfd13f4-ebb9-481b-8020-8af26acbd6df

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Date deposited: 04 Jul 2022 17:19
Last modified: 04 Jul 2022 17:19

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Author: Robin James Forder

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