This thesis descibes n.m.r. spectroscopic studies
of the preparation and reactions of some platinum (II)
halo-phosphine and phosphane species. PtC1H(PEt₃)₂
reacts with PCl₃ in CD₂Cl₂ at 180 K to produce
PtCl (PEt₃)₂ (PCI₂). On warming the solution, reversible
protonation occurs to give [PtCl(PEt₃)₂(PCl₂H)]⁺.
Further warming of the solution results in the formation
of PtCi(PEt₃)₂(PH₂Cl₂). This species is thermally
unstable above 260 K. Reaction of this species with HC1
or BCl₃ results in its dissociation to PtCl(PEt₃)₂(PH₂Cl)
and HCl₂ or [BCl₄]⁻. Analogous behaviour was observed in
the reaction of PtBrH(PEt₃)₂ with PBr₃ except that the
initial six-coordinate product of oxidative addition at
platinum was detected. The mechanism of formation of
these products is discussed.
Isolation of PtCl(PEt₃)₂(PCl₂) as an oil from the
reaction of PtCIH(PEt₃)₂ with PCl₃ in the presence of
Me₃N allowed its chemistry to be studied. A wide range
of reactions was carried out with non-transition metal
species to produce several interesting products.
Reactions with transition metal complexes resulted in the
formation of several hetero and homo-bimetallic species
containing -PCl₂ or -PCI bridging groups.
Attempts were made to produce a species containing
a terminal -PF₂ group by the reaction of PtH₂(PCy₃)₂ with
difluorophosphine species. Although unsucessful, the
resulting cationic species contained -PF₂H groups and
were spectroscopically characterised.
An appendix containing n.m.r. parameters for
complexes of iridium, platinum and rhodium is also