Nucleophilicity of low-valent metal complexes. I. The reactions of platinum(0) complexes with alkyl and acyl halides

Abstract

The nucleophilic behavior of zero-valent platinum complexes toward a variety of covalent molecules has been studied. Although too rapid for convenient kinetic studies to be made, oxidative addition reactions of this type enable a number of novel organo-platinum(II) derivatives to be prepared without the use of conventional organometallic reagents. Cleavage of carbon–halogen bonds in unsaturated molecules of the type —C≡≡CX and CH==CHX is very fast, and the rate of reaction appears to depend little on the electronegativity of the carbon atom to which the halogen is bonded. Similar reactions occur between the zero-valent platinum species and acyl and sulfonyl halides. The S-sulfinate and acyl platinum derivatives, when heated, lose SO 2 and CO, respectively, with the formation of alkyl or aryl platinum complexes.