Abstract
The complexes trans-PdEt2L2 (L = PMe3, PEt3 or PMePh2) reacted with equimolar or twofold molar amounts of H2SiPh2 to produce various bimetallic palladium(II) complexes with bridging diphenylsilyl ligands, [(Me3P)Pd(μ-SiHPh2)]21, (Me3P)Pd(μ-SiHPh2)Pd(PMe3)22 and [LPd(μ-SiHPh2)]2 (L = PEt33 or PMePh24), in moderate to good yields. Similar reactions using H2SiMePh afforded the complexes [LPd(μ-SiHMePh)]2 (L = PMe35 or PEt36). The isolated complexes were characterized by NMR spectroscopy and elemental analyses. Molecular structures of 3 and 5 have been determined by X-ray crystallography and suggest an agostic interaction between the μ-SiHPh2 or μ-SiHMePh group and the Pd. The NMR study of the complexes revealed the bridging co-ordination of the silyl ligand with the Si–H–Pd three-center, two-electron bond in solution similar to that in the solid state. Complex 2 undergoes exchange of the PMe3 ligands on the NMR timescale. The reactions of 2 with CO and HSPh afforded 1 and Pd(SPh)2(PMe3)2, respectively.
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