Please use this identifier to cite or link to this item:
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.
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.
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
Appears in Collections:SPMS Journal Articles

Citations 20

Updated on Jun 13, 2024

Web of ScienceTM
Citations 20

Updated on Oct 25, 2023

Page view(s)

Updated on Jun 15, 2024

Google ScholarTM




Items in DR-NTU are protected by copyright, with all rights reserved, unless otherwise indicated.