Generation,bonding and reactivity of transient zinc-substituted silylenes  

作　　者：Cheng Xu Thayalan Rajeshkumar Laurent Maron Xuebing Leng Yaofeng Chen 

机构地区：[1]State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences,Chinese Academy of Sciences,Shanghai 200032,China [2]Spin-X Institute,School of Chemistry and Chemical Engineering,State Key Laboratory of Luminescent Materials and Devices,Guangdong-Hong Kong-Macao Joint Laboratory of Optoelectronic and Magnetic Functional Materials,South China University of Technology,Guangzhou 510641,China [3]LPCNO,CNRS,&INSA,UniversitéPaul Sabatier,Toulous 31077,France

出　　处：《Science China Chemistry》2024年第4期1256-1262,共7页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(21890721,21732007);the Shanghai Municipal Committee of Science and Technology;the Chinese Academy of Sciences President’s International Fellowship Initiative。

摘　　要：The metal-substituted silylenes are of high interest,as the theoretical studies indicated that the silylenes with electropositive substituents have a small ΔE_(S-T)(singlet-triplet energy gap)or even the ground-state triplets.However,such compounds are highly unstable,and only two transient alkali metal-substituted silylenes M(^(t)Bu_(3)Si)Si:(M=Li,K)were generated by photoextrusion of the alkali metal-substituted silacyclopropenes and merely studied by spectroscopic method(EPR)at low temperature(14 to 50 K).Herein,we report the generation of transient zinc-substituted silylenes from zinc silacyclopropanyl complexes under very mild and convenient conditions.The generated transient zinc-substituted silylenes are highly reactive and undergo intermolecular cycloaddition with alkenes for the synthesis of zinc-substituted Si-heterocyclic compounds.If there is no substrate,the zinc-substituted silylenes attack the C-C bonds of the β-diketiminato ligands and break the C-C bonds.DFT studies further highlight the silylene nature of the zinc-substituted silylene and a very small ΔE_(S-T)(4.4 kcal/mol).

关 键 词：zinc complex SILYLENE C-C bond cleavage CYCLOADDITION DFT calculations 

分 类 号：O641.4[理学—物理化学]