Radicals and biradicals can easily be obtained when Si(IV) compds. are reduced and stabilized by the Lewis base cyclic(alkyl)(amino)carbene (cAAC = C(CH2)(CMe2)2N-Dipp, Dipp = 2,6-i-Pr2C6H3) featuring strong s-donor and p-acceptor properties. To obtain the cAAC-stabilized monoradicals with halogen and alkyl substituents at the Si(IV) atoms, the Ar substituent (Ar = o-C6H4NMe2) was employed to act as a side-arm N donor ligand. The resulting monoradicals ArSiCl2(cAAC) (4) and ArSiRCl(cAAC) (R = Me 5; Et 6) were isolated by the redn. of ArSiCl2 (1) and ArSiRCl2 (R = Me 2; Et 3) with KC8 in the presence of cAAC with a strict ratio of 1:1:1. The three room-temp. stable radicals were kept for at least 3 mo in the solid state under dry N2 atmosphere without decompn. All the compds. were fully characterized by liq. injection field desorption/ionization-mass spectrometry, ESR spectroscopy, UV/visible spectroscopy, elemental anal., and single-crystal x-ray crystallog. studies. [on SciFinder(R)]
%0 Journal Article
%1 Li.2019
%A Li, Wenling
%A Kundu, Subrata
%A Kohler, Christian
%A Li, Jiancheng
%A Dutta, Sayan
%A Yang, Zhi
%A Stalke, Dietmar
%A Herbst-Irmer, Regine
%A Stuckl, A. Claudia
%A Schwederski, Brigitte
%A Koley, Debasis
%A Kaim, Wolfgang
%A Roesky, Herbert W.
%D 2019
%J Organometallics
%K DFT ESR MS;crystal alkylaminocarbene compd compd;mol compd;optimized geometry monoradical organosilicon prepn stabilized structure
%N 9
%P 1939--1945
%R 10.1021/acs.organomet.9b00041
%T Cyclic Alkyl(amino) Carbene-Stabilized Monoradicals of Organosilicon(IV) Compounds with Small Substituents
%V 38
%X Radicals and biradicals can easily be obtained when Si(IV) compds. are reduced and stabilized by the Lewis base cyclic(alkyl)(amino)carbene (cAAC = C(CH2)(CMe2)2N-Dipp, Dipp = 2,6-i-Pr2C6H3) featuring strong s-donor and p-acceptor properties. To obtain the cAAC-stabilized monoradicals with halogen and alkyl substituents at the Si(IV) atoms, the Ar substituent (Ar = o-C6H4NMe2) was employed to act as a side-arm N donor ligand. The resulting monoradicals ArSiCl2(cAAC) (4) and ArSiRCl(cAAC) (R = Me 5; Et 6) were isolated by the redn. of ArSiCl2 (1) and ArSiRCl2 (R = Me 2; Et 3) with KC8 in the presence of cAAC with a strict ratio of 1:1:1. The three room-temp. stable radicals were kept for at least 3 mo in the solid state under dry N2 atmosphere without decompn. All the compds. were fully characterized by liq. injection field desorption/ionization-mass spectrometry, ESR spectroscopy, UV/visible spectroscopy, elemental anal., and single-crystal x-ray crystallog. studies. [on SciFinder(R)]
@article{Li.2019,
abstract = {Radicals and biradicals can easily be obtained when Si(IV) compds. are reduced and stabilized by the Lewis base cyclic(alkyl)(amino)carbene (cAAC = C(CH2)(CMe2)2N-Dipp, Dipp = 2,6-i-Pr2C6H3) featuring strong \textgreek{s}-donor and \textgreek{p}-acceptor properties. To obtain the cAAC-stabilized monoradicals with halogen and alkyl substituents at the Si(IV) atoms, the Ar substituent (Ar = o-C6H4NMe2) was employed to act as a side-arm N donor ligand. The resulting monoradicals ArSiCl2(cAAC) (4) and ArSiRCl(cAAC) (R = Me 5; Et 6) were isolated by the redn. of ArSiCl2 (1) and ArSiRCl2 (R = Me 2; Et 3) with KC8 in the presence of cAAC with a strict ratio of 1:1:1. The three room-temp. stable radicals were kept for at least 3 mo in the solid state under dry N2 atmosphere without decompn. All the compds. were fully characterized by liq. injection field desorption/ionization-mass spectrometry, ESR spectroscopy, UV/visible spectroscopy, elemental anal., and single-crystal x-ray crystallog. studies. [on SciFinder(R)]},
added-at = {2022-06-15T11:26:56.000+0200},
author = {Li, Wenling and Kundu, Subrata and Kohler, Christian and Li, Jiancheng and Dutta, Sayan and Yang, Zhi and Stalke, Dietmar and Herbst-Irmer, Regine and Stuckl, A. Claudia and Schwederski, Brigitte and Koley, Debasis and Kaim, Wolfgang and Roesky, Herbert W.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/28c8dd9e06f8c85cb1f3727f8d478367b/huebleriac},
doi = {10.1021/acs.organomet.9b00041},
interhash = {65462c069bc70f505712193262b32e14},
intrahash = {8c8dd9e06f8c85cb1f3727f8d478367b},
issn = {0276-7333},
journal = {Organometallics},
keywords = {DFT ESR MS;crystal alkylaminocarbene compd compd;mol compd;optimized geometry monoradical organosilicon prepn stabilized structure},
number = 9,
pages = {1939--1945},
timestamp = {2022-06-15T09:26:56.000+0200},
title = {Cyclic Alkyl(amino) Carbene-Stabilized Monoradicals of Organosilicon(IV) Compounds with Small Substituents},
volume = 38,
year = 2019
}