Isolable Anion Radicals of Nitrosoarenes  

作　　者：Dongyang Wang Masilamani Tamizmani Xuebing Leng Liang Deng 

机构地区：[1]State Key Laboratory of Organometallic Chemistry,Center for Excellence in Molecular Synthesis,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,345 Lingling Road,Shanghai 200032,China [2]Shenzhen Grubbs Institute,Southern University of Science and Technology,Shenzhen,Guangdong 518055,China

出　　处：《Chinese Journal of Chemistry》2020年第2期158-162,共5页中国化学（英文版）

基　　金：We sincerely thank the financial support from the National Natural Science Foundation of China(Nos.21725104,21690062,21432001,and 21821002);the National Key Research and Development Program(2016YFA0202900);the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB20000000);the Program of Shanghai Academic Research Leader(19XD1424800).

摘　　要：Summary of main observation and conclusion The rich redox chemistry of nitrosoarenes has rendered these reactive molecules very useful in modern synthetic and material chemistry.Electrochemical studies have revealed the capability of nitrosoarenes to undergo one-electron oxidation or reduction reaction for a long time.However,the isolation and structural characterization of nitrosoarene radical compounds deviating the stabilization of transition-metal have not been achieved.Investigation on the reduction reaction of nitrosoarenes bearing steric demanding substituents has now revealed that the interaction of 2,6-dimesityl-1-nitroso-benzene(DmpNO)or 2,4,6-tri(tert-butyl)-1-nitroso-benzene(TtpNO)with KC8 and crypt-2,2,2 can produce the corresponding anion radical compound[K(crypt-2,2,2)][DmpNO](1)or[K(crypt-2,2,2)][TtpNO](2)in good isolated yield.Compounds 1 and 2 represent the first examples of isolable nitrosoarene radical compounds deviating the stabilization of transition-metal,and have been characterized by single-crystal X-ray diffraction study,electron paramagnetic resonance(EPR)spectroscopy,and elemental analysis.Theoretical study in collaboration with the characterization data revealed that the unpaired spin in[DmpNO]·-and[TtpNO]·-delocalizes on the nitroso and the central phenyl groups.

关 键 词：STABILIZATION RADICAL BENZENE 

分 类 号：O625[理学—有机化学]