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Nonclassical Ruthenium Silyl Dihydride Complexes TpRu(PPh 3 )(η 3 ‐HSiR 3 H) [Tp = Hydridotris(pyrazolyl)borate]: Catalytic Hydrolytic Oxidation of Organosilanes to Silanols with TpRu(PPh 3 )(η 3 ‐HSiR 3 H)
Author(s) -
Lee Ting Yan,
Dang Li,
Zhou Zhongyuan,
Yeung Chi Hung,
Lin Zhenyang,
Lau Chak Po
Publication year - 2010
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.201000951
Subject(s) - chemistry , silylation , hydride , silanes , silane , medicinal chemistry , catalysis , ruthenium , hydrolysis , regioselectivity , boron , stereochemistry , organic chemistry , metal
An X‐ray crystallographic study showed that it is more appropriate to describe the complexes TpRu(PPh 3 )“H 2 SiR 3 ” as TpRu(PPh 3 )(η 3 ‐HSiR 3 H), a static structure containing H ··· Si ··· H bonding rather than a highly fluxional pair ofσ‐silane hydride species TpRu(PPh 3 )(H a )(η 2 ‐H b SiR 3 ) [rlhar2] TpRu(PPh 3 )(H b )(η 2 ‐H a SiR 3 ). One of the complexes was used for the catalytic hydrolytic oxidation of organosilanes to silanols. A mechanism, which does not involve the usual oxidative addition of silane to the metal center to form the silyl hydride species, is proposed, which is supported by theoretical calculations.