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Activation of Si–Si and Si–H Bonds at a Platinum Bis(diphenylphosphanyl)ferrocene (dppf) Complex: Key Steps for the Catalytic Hydrogenolysis of Disilanes
Author(s) -
Kalläne Sabrina I.,
Laubenstein Reik,
Braun Thomas,
Dietrich Maren
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201501210
Subject(s) - chemistry , catalysis , platinum , ferrocene , hydrogenolysis , medicinal chemistry , silylation , norbornene , selectivity , polymer chemistry , stereochemistry , organic chemistry , polymerization , electrochemistry , polymer , electrode
Treatment of the platinum(0) complex [Pt(dppf)(nbe)] [ 1 ; dppf = 1,1′‐bis(diphenylphosphanyl)ferrocene, nbe = norbornene] with the 1,2‐dihydrodisilanes HPh 2 SiSiPh 2 H or HMe 2 SiSiMe 2 H gave [Pt(SiR 2 H) 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 H 2 to give [Pt(H)(SiR 2 H)(dppf)] ( 3 , R = Ph; 5 , R = Me) and H 2 SiR 2 . Adding HPh 2 SiSiPh 2 H to the hydrido silyl complex 3 , which can also be prepared through Si–H activation of H 2 SiPh 2 at 1 , resulted in the regeneration of 2 as well as in the release of H 2 SiPh 2 . Treatment of HR 2 SiSiR 2 H with H 2 (1.7 bar) in the presence of 2 or 4 under moderate conditions led to the catalytic formation of H 2 SiR 2 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.