Abstract
Comproportionation of the platinum(0) complex Pt(PMe{sub 3}){sub 4} with the platinum(II) hexafluoroacetylacetonate complexes Pt(hfac){sub 2} or [Pt(hfac)(PMe{sub 3}){sub 2}][hfac] yields diplatinum species of stoichiometry [Pt{sub 2}({mu}-hfac)(PMe{sub 3}){sub 4}]-[hfac], 1, and [Pt{sub 2}(PMe{sub 3}){sub 6}][hfac]{sub 2}, 2, respectively. The NMR spectra and X-ray crystal structure of 1 show that the two platinum centers are chemically inequivalent; one is square-planar platinum(II) center, and the other is trigonal planar platinum(0) center. One of the hfac groups is anionic while the other bridges between the two platinum atoms. Each platinum center bears two PMe{sub 3} ligands, and the bridging hfac group, however, is bound to the other platinum center as an {eta}{sup 2} alkene ligand via its methine carbon and one of the two carbonyl carbons. The two platinum atoms do not interact directly with one another and are separated by 3.786(1) {angstrom}. The {sup 1}H NMR spectra of the hexakis(trimethylphosphine) diplatinum complex 2 are consistent with a structure in which the two platinum centers are connected by a Pt-Pt bond and the six PMe{sub 3} groups complete two mutually perpendicular square-planar coordination environments. Treatment of Pt(PMe{sub 3}){sub 4}. 57 refs., 4 figs., 2 tabs.
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