Pyrolysis of diaryl(phosphine)platinum(II) complexes: reductive elimination followed by subsequent decomposition of the platinum-containing residue

Abstract
The condensed-phase thermolyses of complexes [PtR2L2] and [PtR2(P–P)][R = Ph or C6H4Me-4; L = PPh3 or P(C6H4Me-4)3; P–P = Ph2PC2H4PPh2(dppe) or Ph2PCH2PPh2(dppm)] have been examined by t.g.a., d.t.a., d.s.c., and product analysis. The primary decomposition step is concerted reductive elimination forming R2. Experiments on mixtures established both that this elimination is intramolecular, and that no scrambling of ligands occurs priorto pyrolysis. Secondary decompositions of [PtL2] and [Pt(P–P)] give reproducible but non-stoicheiometric amounts of biaryl and arene, probably via insertion of Pt0 into aryl–phosphorus and –hydrogen bonds followed by eliminations from Pt. Red-brown glassy residues remain. The mechanisms of these steps and the nature of the residues are discussed.

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