THERMAL GENERATION OF BIS(TRIETHYLPHOSPHINE)-3,3-DIMETHYLPLATINACYCLOBUTANE FROM DINEOPENTYLBIS(TRIETHYLPHOSPHINE)PLATINUM(II)

Reactions which cleave unactivated aliphatic carbon-hy-drogen bonds are important in a range of heterogeneous platinum-catalyzed transformations of hydrocarbons, and a mechanistic understanding of these types of reactions is one objective of current research in catalysis.2 The mechanisms of heterogeneous reactions are difficult to examine directly. Here we outline the mechanism of a tractable and well-defined solution reaction—the conversion of dineopentylbis(triethylphosphine)platinum(II) (1) to bis(triethylphosphine)-3, 3-dimethylplatinacyclobutane (4)—which involves cleavage of an unactivated C-H bond by intramolecular oxidative addition to a soluble platinum species. This mechanism establishes certain of the structural features which facilitate C-H bond activation in solution and suggests, by analogy, possible characteristics of the heterogeneous reactions. © 1979, American Chemical Society. All rights reserved.