Please use this identifier to cite or link to this item: https://hdl.handle.net/10356/159525
Title: Si(II) cation-promoted formation of an abnormal NHC-bound silylene and a cAAC-silanyl radical ion
Authors: Zhu, Keke
Dutta, Sayan
Han, Weichun
Wang, Chenfeng
Lee, Jiawen
Tan, Gengwen
Koley, Debasis
So, Cheuk-Wai
Li, Yan
Keywords: Science::Chemistry
Issue Date: 2021
Source: Zhu, K., Dutta, S., Han, W., Wang, C., Lee, J., Tan, G., Koley, D., So, C. & Li, Y. (2021). Si(II) cation-promoted formation of an abnormal NHC-bound silylene and a cAAC-silanyl radical ion. Inorganic Chemistry, 60, 7143-7149. https://dx.doi.org/10.1021/acs.inorgchem.1c00188
Journal: Inorganic Chemistry
Abstract: The reaction of amidinatosilylene LSi(:)Cl [L = PhC(NtBu)2] with N-heterocyclic carbene IAr [:C{N(Ar)CH}2, where Ar = 2,6-iPr2C6H3] and NaOTf in tetrahydrofuran (THF) facilely afforded a silicon(II) cation [LSi(:)-aIAr]+OTf- (1+OTf-), where IAr isomerizes to abnormal N-heterocyclic carbene aIAr, coordinating to the silicon(II) center. Its Ge homologue, [LGe(:)-aIAr]+OTf- (2+OTf-), was also accessed via the same protocol. For the formation of 1+, we propose that an in situ-generated Si(II) cation [LSi(:)]+ under the treatment of LSi(:)Cl with NaOTf may isomerize IAr in THF. In contrast, the replacement of IAr with cyclic alkyl(amino) carbene (cAAC) furnished a cAAC-silanyl radical ion [LSi(H)-cAAC]•+(LiOTf2)- [3•+(LiOTf2)-], which may undergo an abstraction of the H radical from THF. All of the products were characterized by nuclear magnetic resonance spectroscopy, electron paramagnetic resonance, and X-ray crystallography, and their bonding scenarios were investigated by density functional theory calculations. These studies provide new perspective on carbene-silicon chemistry.
URI: https://hdl.handle.net/10356/159525
ISSN: 0020-1669
DOI: 10.1021/acs.inorgchem.1c00188
Schools: School of Physical and Mathematical Sciences 
Rights: © 2021 American Chemical Society. All rights reserved.
Fulltext Permission: none
Fulltext Availability: No Fulltext
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