首页|An Isolable Phosphinogermylyne as a Synthon of One-Coordinate GeⅠ Radical

An Isolable Phosphinogermylyne as a Synthon of One-Coordinate GeⅠ Radical

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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 GeⅠ radical center,acyclic two-coordinate GeⅠ radicals 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.

PhosphinogermylyneGermaniumRadicalsDonor-acceptor systemsRadical reactions

Dongmin Wang、Haonan Chen、Yuhao He、Xiaodan Chen、Li Zhang、Gengwen Tan

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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

Innovation Center for Chemical Science,College of Chemistry,Chemical Engineering and Materials Science,Soochow University,Suzhou,Jiangsu 215123,China

College of Chemistry and Material,Jinan University,Guangzhou,Guangdong 510632,China

School of Electronic Engineering,Guangxi University of Science and Technology,Liuzhou,Guangxi 545000,China

Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education,Hangzhou Normal University

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国家自然科学基金国家自然科学基金Fundamental Research Funds for the Central Universities,Sun Yatsen UniversitySuzhou Science and Technology NOVA ProgramGuangxi University of Science and TechnologyGuangxi University of Science and TechnologyGuangxi Department of Science and Technology

223221122207116423qnpy35ZXL202244503190227031902282021GXNSFBA220021

2024

10.1002/cjoc.202300581

中国化学(英文版)
中国化学会 上海有机化学研究所

中国化学(英文版)

CSTPCD
影响因子：0.848
ISSN：1001-604X
年,卷(期)：2024.42(7)
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