Construction of a low-valent thiolate-bridged dicobalt platform and its reactivity toward hydrogen activation and evolution  

作　　者：Tao Mei Dawei Yang Linan Su Baomin Wang Jingping Qu 

机构地区：[1]State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,China

出　　处：《Chinese Chemical Letters》2022年第5期2477-2480,共4页中国化学快报（英文版）

基　　金：supported by the National Natural Science Foun-dation of China(Nos.21690064,22001031);Key Laboratory of Bio-based Chemicals of Liaoning Province of China,the“111”project of the Ministry of Education of China and the Fundamental Research Funds for the Central Universities(No.DUT19RC(3)013).

摘　　要：Low-valence transition metallic complexes have drawn longstanding attention due to their high reactivity toward catalytic transformation of various small molecules.Among these known complexes,the low-valence metal centres are commonly stabilized by neutral bulky ligands with strong electron-donating capacity.However,low-valence bimetallic complexes supported by anionic sulfur and cyclopentadienyl ligands are still difficult to obtain in high isolated yield.Herein,we report the synthesis and characteri-zation of two scarce thiolate-bridged Co^(I)Co^(II)and Co^(I)Co^(I)complexes bearing sterically demanding ligands through two stepwise one-electron reduction processes.Interestingly,the Co^(I)Co^(II)complex can facilely promote the homolytic cleavage of dihydrogen across the short Co−Co metallic bond to give a Co^(II)Co III dihydride bridged complex,which is capable of serving as a competent hydrogen atom transfer agent.Moreover,the anionic Co^(I)Co^(I)complex can trigger a stepwise hydrogen generation cycle involving several isolated and structurally well-characterized intermediates.

关 键 词：Low-valence Thiolate-bridged Cobalt Homolytic H_(2)cleavage HYDRIDE Hydrogen evolution 

分 类 号：O641.4[理学—物理化学]