An Isolable Phosphinogermylyne as a Synthon of One-Coordinate GeⅠRadical  

作　　者：Dongmin Wang Haonan Chen Yuhao He Xiaodan Chen Li Zhang Gengwen Tan 

机构地区：[1]Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education,Guangdong Basic Research Center of Excellence for Functional Molecular Engineering,School of Chemistry,IGCME,Sun Yat-Sen University,Guangzhou,Guangdong 510275,China [2]School of Electronic Engineering,Guangxi Universityof Science and Technology,Liuzhou,Guangxi 545000,China [3]College of Chemistry and Material,Jinan University,Guangzhou,Guangdong 510632,China [4]Innovation Center for Chemical Science,College of Chemistry,Chemical Engineering and Materials Science,Soochow University,Suzhou,Jiangsu 215123,China [5]Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education,Hangzhou Normal University,Hangzhou,Zhejiang 311121,China

出　　处：《Chinese Journal of Chemistry》2024年第7期736-742,共7页中国化学（英文版）

基　　金：National Natural Science Foundation of China (Grants:22322112 and 22071164);Fundamental Research Funds for the Central Universities,Sun Yat-sen University (23qnpy35);the Suzhou Science&Technology NOVA Program (Grant:ZXL2022445)for generous financial support;L.Z.thanks Guangxi University of Science and Technology (03190227 and 03190228);the Guangxi Department of Science and Technology (2021GXNSFBA220021)for financial support.

摘　　要：Reduction of chlorogermylene MsFluindtBu-GeCl 1 with potassium graphite(KC8)afforded putative germylyne radical MsFluindtBu-Ge 2 as confirmed by electron paramagnetic resonance(EPR)spectroscopy.However,it slowly decayed via C—H bond activation at the fluorenyl moiety to yield a bis(germylene)3 at room temperature.By using a Lewis base to stabilize the unoccupied p orbital at the GeⅠradical center,acyclic two-coordinate GeⅠradicals MsFluindtBu-Ge(IMe4)4(IMe4=1,3,4,5-tetramethyl-imidazolin-2-ylidene),MsFluindtBu-Ge(IiPr)5(IiPr=1,3-diisopropyl-4,5-dimethyl-imidazolin-2-ylidene),MsFluindtBu-Ge(PMe3)6 were isolated in crystalline forms.The unpaired electron in 4-6 mainly resides at the Ge 4p orbital as revealed by EPR spectroscopic studies and theoretical calculations.Interestingly,facile ligand exchange of PMe3 in 6 with IMe4 and IiPr was observed to afford 4 and 5,respectively.Moreover,phosphinogermylyne 6 reacted with PhEEPh(E=S,Se),4-tetrabutylphenylacetylene(Ar'CCH),[CpMo(CO)3]2 and nBu3SnH to furnish germylenes MsFluindtBu-GeEPh(E=S 7,Se 8),MsFluindtBu-GeCH=CHAr'9,a germylyne complex MsFluindtBu-Ge≡Mo(CO)2Cp 10 and a Ge(Ⅳ)compound MsFluindtBu-GeH2SnnBu311,respectively.The reactivity studies demonstrate that 6 can act as a synthon of one-coordinate germylyne radical attributing to labile coordination of trimethylphosphine.

关 键 词：Phosphinogermylyne GERMANIUM RADICALS Donor-acceptor systems Radical reactions 

分 类 号：O62[理学—有机化学]