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Abstract
The preparation and characterization of new osmium(II) and osmium(IV) silyl derivatives containing the cyclopentadienyl(phosphine) and pentamethylcyclopentadienyl(phosphine) ligand sets are described. The osmium silyl complexes are prepared by thermal reactions of hydrosilanes with osmium(II) alkyl complexes of the type Cp‘(PR3)2OsCH2SiMe3 (Cp‘ = Cp, R = Ph (4), Me (5); Cp‘ = η5-C5Me5, R = Me (7)), which in turn are available via alkylation of the corresponding bromo complexes. The synthesis of alkyl derivatives of Cp(PR3)2Os (R = Ph, Me) requires the use of dialkylmagnesium reagents, while alkylation of the more electron-rich Cp*(PMe3)2Os system can be achieved using Grignard reagents. Additionally, reaction of Cp(PPh3)2OsBr with AgOTf (Tf = SO2CF3) affords the osmium(II) triflate complex Cp(PPh3)2OsOTf (2), which possesses a labile triflate group. The structure of complex 2 was determined by X-ray crystallography. Similar to their ruthenium analogs, the osmium(II) alkyl complexes 4, 5, and 7 thermally a...
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