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Interconversion of 42and 44-Electron Platinum triangulo-Clusters using Chelating Tertiary Phosphine Ligands and the Structural Characterisation t of [I ,3-B is( d i phenyl p hosph i no) propane] -tris (p-su I phu r dioxide)bis( tricyclohexyl-ph0sphine)triplatinum-Benzene (1 /2), [Pt3(p-S02)3{P(C,H,,),},(dppp)]~2C6H6

The reduction of cis- [ PtCI,( CO) (PR,)] (R = a variety of alkyl or aryl groups) by zinc dust or sodium tetrahydroborate under a carbon monoxide atmosphere is an efficient high-yield method for the formation of tri-, tetra-, and penta-nuclear clusters, which is superior in yield, convenience, and generality to other methods. The nuclearity of the cluster formed appears to be the result of a subtle interplay between the steric and electronic properties of the phosphine and, in the case of triphenylphosphine at least, is altered by the presence of free ligand. Reactions of some of the above clusters with the unsaturated inorganic molecules SO, , CS, , and COS are reported. In some reactions the initial cluster framework is retained with concomitant complete or partial substitution of the bridging carbonyl ligands but in other cases either cluster aggregation or degradation is observed. 449 P2S2')/p.p.m. 61.9 2J(Pt2P2')/Hz 30 1 ' J( Pt I P ) i H z 5 134 '4 P' P2)/Hz 51 'J(Pt2P2iHz 4 055 3J( P2P2')/Hz 62 'J( Pt I P2)/Hz 372 (5) (6) P)/p.p.m. 29.2 21.1 ' J ( PtP)/Hz 3 854 3 161 3J( PP)/Hz 67 149 'J( Pt P)/Hz 297 122

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