Trinuclear μ3‑Silyl Complexes of Ruthenium and Group 9 Metals Having 3c-2e Interactions and Transformation of a μ3‑Silyl Complex of Ru2Ir into μ‑Silyl and μ3‑Silylene Complexes

μ3-Silyl complexes (Cp*Ru)2(Cp*M)­(μ3-H2SiR)­(μ-H)3 (4, M = Co; 5, M = Rh; 6, M = Ir) were synthesized by the reaction of trinuclear heterometallic clusters of Ru and group 9 metals, (Cp*Ru)2(Cp*M)­(μ-H)3(μ3-H) (1, M = Co; 2, M = Rh; 3, M = Ir), with primary silanes. The unprecedented coordination mode of primary silanes on a trimetallic plane was unambiguously confirmed by means of multinuclear NMR spectroscopy, IR spectroscopy, and X-ray diffraction studies. The μ-silane complex (Cp*Ru)2(Cp*Ir)­(μ-H2SiHtBu)­(μ-H)4 (7), which is a plausible intermediate en route to the μ3-silyl complex, was obtained by the reaction of 3 with tBuSiH3. The μ3-silyl complex 6a was transformed into the μ-silyl complex (Cp*Ru)2(Cp*Ir)­(μ-H2SiPh)­(tBuNC)­(μ-H)3 (8) upon treatment with tBuNC. Complex 6a also reacted with CO to afford the μ3-silylene complex (Cp*Ru)2(Cp*Ir)­(μ3-HSiPh)­(μ-CO)­(μ-H)2 (10) via the formation of the μ-silyl complex (Cp*Ru)2(Cp*Ir)­(μ-H2SiPh)­(CO)­(μ-H)3 (9).