In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2016, No. 17 ( 2016-06), p. 2696-2703
Abstract:
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.
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2016.17
DOI:
10.1002/ejic.201600355
Language:
English
Publisher:
Wiley
Publication Date:
2016
detail.hit.zdb_id:
1475009-0
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