TY - JOUR
T1 - Cyclic Alkyl(amino) Carbene-Stabilized Monoradicals of Organosilicon(IV) Compounds with Small Substituents
AU - Li, Wenling
AU - Kundu, Subrata
AU - Köhler, Christian
AU - Li, Jiancheng
AU - Dutta, Sayan
AU - Yang, Zhi
AU - Stalke, Dietmar
AU - Herbst-Irmer, Regine
AU - Stückl, A. Claudia
AU - Schwederski, Brigitte
AU - Koley, Debasis
AU - Kaim, Wolfgang
AU - Roesky, Herbert W.
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/5/13
Y1 - 2019/5/13
N2 - Radicals and biradicals can easily be obtained when silicon(IV) compounds 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 σ-donor and π-acceptor properties. To obtain the cAAC-stabilized monoradicals with halogen and alkyl substituents at the silicon(IV) atoms, the Ar substituent (Ar = o-C6H4NMe2) was employed to act as a side-arm nitrogen donor ligand. The resulting monoradicals ArSiCl2(cAAC) (4) and ArSiRCl(cAAC) (R = Me 5; Et 6) were isolated by the reduction 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-temperature stable radicals were kept for at least 3 months in the solid state under dry N2 atmosphere without decomposition. All the compounds were fully characterized by liquid injection field desorption/ionization-mass spectrometry, electron paramagnetic resonance spectroscopy, UV/vis spectroscopy, elemental analysis, and single-crystal X-ray crystallographic studies.
AB - Radicals and biradicals can easily be obtained when silicon(IV) compounds 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 σ-donor and π-acceptor properties. To obtain the cAAC-stabilized monoradicals with halogen and alkyl substituents at the silicon(IV) atoms, the Ar substituent (Ar = o-C6H4NMe2) was employed to act as a side-arm nitrogen donor ligand. The resulting monoradicals ArSiCl2(cAAC) (4) and ArSiRCl(cAAC) (R = Me 5; Et 6) were isolated by the reduction 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-temperature stable radicals were kept for at least 3 months in the solid state under dry N2 atmosphere without decomposition. All the compounds were fully characterized by liquid injection field desorption/ionization-mass spectrometry, electron paramagnetic resonance spectroscopy, UV/vis spectroscopy, elemental analysis, and single-crystal X-ray crystallographic studies.
UR - http://www.scopus.com/inward/record.url?scp=85065673245&partnerID=8YFLogxK
U2 - 10.1021/acs.organomet.9b00041
DO - 10.1021/acs.organomet.9b00041
M3 - Article
AN - SCOPUS:85065673245
SN - 0276-7333
VL - 38
SP - 1939
EP - 1945
JO - Organometallics
JF - Organometallics
IS - 9
ER -