NDLI: Mechanism of the cooperative Si–H bond activation at Ru

Content Provider	Royal Society of Chemistry (RSC)
Author	Königs, C. David F. Oestreich, Martin Tatsumi, Kazuyuki Stahl, Timo Ohki, Yasuhiro Kaupp, Martin Hrobárik, Peter Klare, Hendrik F. T. Kemper, Sebastian
Copyright Year	2015
Abstract	The nature of the hydrosilane activation mediated by ruthenium(II) thiolate complexes of type [(R3P)Ru(SDmp)]+[BArF4]− is elucidated by an in-depth experimental and theoretical study. The combination of various ruthenium(II) thiolate complexes and tertiary hydrosilanes under variation of the phosphine ligand and the substitution pattern at the silicon atom is investigated, providing detailed insight into the activation mode. The mechanism of action involves reversible heterolytic splitting of the Si–H bond across the polar Ru–S bond without changing the oxidation state of the metal, generating a ruthenium(II) hydride and sulfur-stabilized silicon cations, i.e. metallasilylsulfonium ions. These stable yet highly reactive adducts, which serve as potent silicon electrophiles in various catalytic transformations, are fully characterized by systematic multinuclear NMR spectroscopy. The structural assignment is further verified by successful isolation and crystallographic characterization of these key intermediates. Quantum-chemical analyses of diverse bonding scenarios are in excellent agreement with the experimental findings. Moreover, the calculations reveal that formation of the hydrosilane adducts proceeds via barrierless electrophilic activation of the hydrosilane by sterically controlled η1 (end-on) or η2 (side-on) coordination of the Si–H bond to the Lewis acidic metal center, followed by heterolytic cleavage of the Si–H bond through a concerted four-membered transition state. The Ru–S bond remains virtually intact during the Si–H bond activation event and also preserves appreciable bonding character in the hydrosilane adducts. The overall Si–H bond activation process is exergonic with ΔG0r ranging from −20 to −40 kJ mol−1, proceeding instantly already at low temperatures.
Starting Page	4324
Ending Page	4334
Page Count	11
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	6
Issue Number	7
Journal	Chemical Science
DOI	10.1039/c5sc01035g
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	Ruthenium Phosphine Ligand Chemical bond Lewis Exergonic process Nuclear magnetic resonance spectroscopy Hydride Electrophile
Content Type	Text
Resource Type	Article
Subject	Chemistry

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