Cyclic Alkyl(amino) Carbene-Stabilized Monoradicals of Organosilicon(IV) Compounds with Small Substituents

被引:7
作者
Li, Wenling [1 ,2 ]
Kundu, Subrata [2 ]
Koehler, Christian [2 ]
Li, Jiancheng [2 ]
Dutta, Sayan [4 ]
Yang, Zhi [1 ]
Stalke, Dietmar [2 ]
Herbst-Irmer, Regine [2 ]
Stueckl, A. Claudia [2 ]
Schwederski, Brigitte [3 ]
Koley, Debasis [4 ]
Kaim, Wolfgang [3 ]
Roesky, Herbert W. [2 ]
机构
[1] Beijing Inst Technol, Sch Chem & Chem Engn, Beijing 102488, Peoples R China
[2] Georg August Univ Gottingen, Inst Anorgan Chem, Tammannstr 4, D-37077 Gottingen, Germany
[3] Univ Stuttgart, Inst Anorgan Chem, D-70569 Stuttgart, Germany
[4] Indian Inst Sci Educ & Res IISER Kolkata, Dept Chem Sci, Mohanpur 741246, India
基金
新加坡国家研究基金会;
关键词
MAIN-GROUP ELEMENTS; STABLE RADICALS; SI-H; APPROXIMATION; SILYLENE; DENSITY; ENERGY; PHOSPHORUS; COMPLEXES; BONDS;
D O I
10.1021/acs.organomet.9b00041
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
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)(2)N-Dipp, Dipp = 2,6-i-Pr2C6H3) featuring strong sigma-donor and pi-acceptor properties. To obtain the cAAC-stabilized monoradicals with halogen and alkyl substituents at the silicon(IV) atoms, the Ar substituent (Ar = o-C6H(4)NMe(2)) 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 N-2 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.
引用
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页码:1939 / 1945
页数:7
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