title: Reactivity of [1],[1]disilamolybdenocenophane toward zerovalent platinum complexes.
abstract: The results of studies of the reactivity of strained [1],[1]disilamolybdenocenophane toward zerovalent platinum complexes are reported. Whereas [Pt(PEt(3))(3)] underwent clean insertion into both Si-C(ispo) bonds of the twofold-bridged molybdenocene, the reaction with the tricyclohexylphosphine analogue is considerably more complex. Thus, treatment of the molybdenum compound with 2 equiv of [Pt(PCy(3))(2)] results in a trinuclear cluster. To gain insight into the mechanistic aspects, the reaction was performed in a 1:1 stoichiometry. Multinuclear NMR spectroscopy revealed the presence of different species in solution. Two constitutional isomers were identified by X-ray diffraction analyses, one presumably depicting an intermediate in the formation of the trinuclear cluster. The predominant isomer in solution was identified as the product of C-H oxidative addition to the platinum phosphine fragment. Its solid-state structure displays an unusual coordination mode of platinum, and structural parameters suggest the formulation as the sigma-complex of a Mo-Si bond.
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Germany. h.braunschweig@mail.uni-wuerzburg.de
authors.forename: Holger
authors.initials: H
authors.lastname: Braunschweig
authors.forename: Peter
authors.initials: P
authors.lastname: Brenner
authors.forename: Manuela
authors.initials: M
authors.lastname: Gross
authors.forename: Krzysztof
authors.initials: K
authors.lastname: Radacki