Use this URL to cite or link to this record in EThOS: https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.373385
Title: Synthetic, structural and spectroscopic studies on some platinum group metal complexes
Author: McAslan, Ewan Blyth
ISNI:       0000 0001 3622 5007
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1986
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Abstract:
Chapter 1: A brief survey of the chemistry of some tertiary phosphine complexes of rhodium, iridium and ruthenium. Chapter 2: A study of the products obtained by the reaction of RhCl₃.3H₂O with various ratios of PEt₂ Ph is reported. Alternative high yield routes to the species [Rh₂Cl₆ (PR₃)₃] 1 (PR₃ = PMe₂Ph, PEt₂Ph and PPrⁿ₂Ph) are described. The synthesis and characterisation of the compounds [Rh₂Cl₅ (PR₃)₄]-BPh₄ are presented and possible mechanisms of formation are discussed. The isolation and characterisation, by physical and chemical methods together with an X-ray crystal structural analysis, of solvated monomer mer-[RhCl₃(PEt₂ Ph)₂ (H₂O)] are reported. The variable temperature ³¹P-{¹H} n.m.r. spectra of the various species are discussed. A scheme linking the various complexes is presented. Chapter 3: Attempts to prepare iridium analogues of the species discussed in chapter 2 are described. Instead of the desired products mer- [IrI₃ (PMe₂Ph)₂ - (NH₃)] was formed. The synthesis and characterisation by physical and chemical methods are reported together with an X-ray crystal structural analysis. Chapter 4: A brief survey of the various preparations used in the synthesis of complexes containing the [(R₂ PO)₂H⁻] and [(R₂PO)₃H₂]⁻ ligands is given. Chapter 5: The alternative routes resulting in the synthesis and characterisation of [RhCl (NO₃){(Ph₂PO)₃ H₂} ] are described. The synthesis and characterisation of the five-coordinated species [Rh(L₂){ (Ph₂PO)₃Na(OH₂)ₓ}] (x = 1,2) prepared by the reaction of [RhCl(N0₃){(Ph₂PO)₃H₂}] with various bidentate ligands L₂ [L₂-(S₂CNMe₂)⁻, (S₂ CNEt₂)⁻ (S(O)CPh)⁻, (O₂CPh)⁻ and (O₂C-C₆H₄-4-CH₃)⁻] are reported. The X-ray crystal structures of [RhCl{ (Ph₂PO)₃H₂}].Ph₂ P(O)H and [Rh(S₂CNEt₂) { (Ph₂PO)₃Na(OH₂) (μ-OH₂)}]₂.4CHCl₃ are presented. Chapter 6 : The reaction of cis-[Ru(S₂PMe₂)₂ (PPh₃)₂] with hydrolysed Ph₂PCl in MeOH/H₂O (7:1, v/v) is reinvestigated. Prolonged reaction generates trans-[RuCl₂ (Ph₂PH)₄] via [Ru(S₂PMe₂ ){ (Ph₂PO)₃H₂} ] and possible mechanisms of formation are discussed. The X-ray crystal structure of trans-[RuCl₂ (Ph₂PH)₄]. 2CHCl₃ is presented.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.373385  DOI: Not available
Keywords: Inorganic chemistry
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