Effects of ancillary ligands in acceptorless benzyl alcohol dehydrogenation mediated by phosphine-free cobalt complexes

作     者：Yan Xu Lu Wang Junwei Wu Guanzhong Zhai Daohua Sun Yan Xu;Lu Wang;Junwei Wu;Guanzhong Zhai;Daohua Sun

作者机构：Department of Chemical and Biochemical EngineeringCollege of Chemistry and Chemical EngineeringXiamen UniversityXiamen 361005China Department of Chemical and Biochemical EngineeringNational Engineering Laboratory for Green Chemical Productions of Alcohols−Ethers−EstersCollege of Chemistry and Chemical EngineeringXiamen UniversityXiamen 361005China Luoyang Ship Material InstituteLuoyang 471039China 

出 版 物：《Frontiers of Chemical Science and Engineering》 (化学科学与工程前沿（英文版）)

年 卷 期：2023年第17卷第3期

页      面：314-325页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：supported by the National Natural Science Foundation of China(Grant No.22078269) 

主　　题：acceptorless alcohol dehydrogenation η^(5)-C_(5)Me_(5)-Co metal-ligand cooperation theoretical calculation 

摘      要：Acceptorless alcohol dehydrogenation stands out as one of the most promising strategies in hydrogen storage *** various catalytic systems for this reaction,cost-effective molecular catalysts using phosphine-free ligands have gained considerable ***,the central challenge for using non-precious metals is to overcome the propensity of reacting by oneelectron ***,we synthesized a phosphine-freeη^(5)-C_(5)Me_(5)-Co complex by using the metal-ligand cooperative strategy and compared its activity with analogous catalysts toward acceptorless alcohol *** catalyst showed excellent performance with a turnover number of 130.4 and a selectivity close to 100%.The improved performance among the class ofη^(5)-C_(5)Me_(5)-Co complexes could be attributed to the more accessible Co center and its cooperation with the redox-active *** further study the systematic structure-activity relationship,we investigated the electronic structures ofη^(5)-C_(5)Me_(5)-Co complexes by a set of *** results showed that the redox-active ligand has a significant influence on theη^(5)-C_(5)Me_(5)-Co *** the meantime,the proximal O−/OH group is beneficial for shuttling *** the catalytic cycle,two dehydrogenation scenarios were interrogated through density functional theory,and the result suggested that the outer-sphere pathway was *** formation of a dihydrogen complex was the rate-determining step with aΔG value of 16.9 kcal∙mol‒*** electron population demonstrated that theη^(5)-C_(5)Me_(5)ligand played a key role in stabilizing transition states during dehydrogenation *** work identified the roles of vital ligand components to boost catalytic performance and offered rationales for designing metal-ligand cooperative nonprecious metal complexes.