Activation of Si–Si and Si–H Bonds at a Platinum Bis(diphenylphos­phanyl)ferrocene (dppf) Complex: Key Steps for the Catalytic Hydro­genolysis of Disilanes

Abstract

AbstractTreatment of the platinum(0) complex [Pt(dppf)(nbe)] [1; dppf = 1,1′‐bis(diphenylphosphanyl)ferrocene, nbe = norbornene] with the 1,2‐dihydrodisilanes HPh2SiSiPh2H or HMe2SiSiMe2H gave [Pt(SiR2H)2(dppf)] (2, R = Ph; 4, R = Me) by oxidative addition of the Si–Si bond. The bis‐silyl complexes 2 and 4 react with H2 to give [Pt(H)(SiR2H)(dppf)] (3, R = Ph; 5, R = Me) and H2SiR2. Adding HPh2SiSiPh2H to the hydrido silyl complex 3, which can also be prepared through Si–H activation of H2SiPh2 at 1, resulted in the regeneration of 2 as well as in the release of H2SiPh2. Treatment of HR2SiSiR2H with H2 (1.7 bar) in the presence of 2 or 4 under moderate conditions led to the catalytic formation of H2SiR2 with TONs up to 25. The catalytic conversions are distinguished by a high selectivity for the hydrogenolysis of the 1,2‐dihydrodisilanes, and no significant tendency for redistribution reactions at Si was observed.