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.
