Abstract
Structure and Reactivity Relationships in Methyl and Hydrido Complexes of Platinum(II) by Group 15 Donor Atom Ligands
Highlights
S QUARE-PLANAR substitution reactions in general follow an associative mode of activation almost without exception, specific examples displaying a dissociative activation have been verified.[1,2]
The route utilising the COD complex was prefered based on the stability of [PtMeCl(COD)] over that of trans-[PtMeCl(SMe2)2]
[PtMeCl(COD)] as reactant necessitates an appreciable excess of the entering ligand to ensure that monomeric complexes are formed in preference to bridging dinuclear species. [33,34,35] The chlorido for iodide substitution in chloroform solution was confirmed by in situ measurements of representative solutions utilising multi nuclear NMR spectroscopy; in all cases well behaved conversions were observed with no detectable side reactions
Summary
S QUARE-PLANAR substitution reactions in general follow an associative mode of activation almost without exception, specific examples displaying a dissociative activation have been verified.[1,2] Steric and electronic factors usually favour the addition of a fifth ligand to form a five-coordinate 18 electron transition state and usually show a considerable extent of discrimination between different entering nucleophiles. Other than substitution, involving squareplanar complexes that proceed through three coordinated transition states include the uncatalysed cis to trans isomerisation of complexes of the type cis-[PtRX(PEt3)2] (R = alkyl or aryl, X = solvent molecule or halide ion).[5] These complexes undergo dissociation of the solvent molecule, or halide ion, to form a 14 electron three-coordinate intermediate which rearranges to the trans isomer and undergoes recombination with the dissociated ligand to form the four-coordinate product. Other reactions include β-hydride elimination from symmetrical and unsymmetrical dialkylbisphosphino platinum(II) complexes,[6] insertion reactions of olefins and carbon monoxide[7] as well as alkyl for halogen exchange reactions,[8] for example between [Pt(Cl)2(SMe2)2] and [Pt(Me)2(SMe2)2]
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