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Reactivity of an N‐Heterocyclic Carbene Stabilized Hydrosilylene towards a Ketone and CO2: Experimental and Theoretical Study
Author(s) -
Eisenhut Carsten,
Breit Nora C.,
Szilvási Tibor,
Irran Elisabeth,
Inoue Shigeyoshi
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.201600355
Subject(s) - chemistry , carbene , reactivity (psychology) , hydrosilylation , benzophenone , ketone , medicinal chemistry , bicyclic molecule , yield (engineering) , transition metal , stereochemistry , catalysis , photochemistry , organic chemistry , medicine , materials science , alternative medicine , pathology , metallurgy
The reaction of N‐heterocyclic carbene (NHC)‐stabilized hydrosilylene 1 , t Bu 3 SiSi(H)←NHC, with one and two equivalents of benzophenone gave rise to bicyclic compounds 2 and 3 , t Bu 3 Si(R)[Si‐CH 2 ‐N(CMeCMeNMe)‐CPh 2 ‐O] (R = H, OCHPh 2 ). The NHC plays a crucial role in this reactivity, as it is directly involved in C–C bond formation and supplies the C–H‐activated methyl group. In the formation of 3 , the terminal Si–H bond of the hydrosilylene is involved in transition‐metal‐free hydrosilylation. All steps in these mechanisms are based on NHC‐stabilized zwitterionic transition states and intermediates and were investigated by utilizing DFT calculations. In addition, the CO 2 activation of 1 to yield cis/trans ‐cyclotrisiloxane 4 , [( t Bu 3 Si)(H)Si‐O] 3 , stereoselectively and its mechanistic study are reported.