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Exclusive 1.4-addition of tetramethyldiphosphine to butadiene occurs slowly above 100"; the reaction is catalysed by azobis(isobutyronitri1e). The formation of cis-and trans-l,4-bis(dimethylphosphino) but-2-ene is discussed in terms of a dimethylphosphino-radical addition involving an allyl radical intermediate, the more reactive primary carbon atom of which abstracts Me,p from the diphosphine. The isomers have been identified by a comparison of their l H n.m.r. spectra with that of the independently prepared trans-compound. The i.r. spectra of the isomers are recorded. Complexes of both isomers with PtII are apparently polymeric; they have been separated by use of their solubility difference. P.O. Box

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