Carbonylation Reactions of a Metallapentalyne:Synthesis of Its Ester and Amide Derivatives  

作　　者：Yongfa Zhu Dafa Chen Ming Luo Haiping Xia 

机构地区：[1]State Key Laboratory of Physical Chemistry of Solid Surfaces,Collaborative Innovation Center of Chemistry for Energy Materials(iChEM),College of Chemistry and Chemical Engineering,Xiamen University,Xiamen,Fujian 361005,China [2]Shenzhen Grubbs Institute,Department of Chemistry,Southern University of Science and Technology,Shenzhen,Guangdong 518055 China

出　　处：《Chinese Journal of Chemistry》2024年第22期2765-2772,共8页中国化学（英文版）

基　　金：supported by the National Natural Science Foundation of China(Nos.92156021,22350009,22101115 and 22371111);Financial Support for Outstanding Talents Training Fund in Shenzhen,the Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002);high level of special funds(G03050k003);Introduction of Major Talent Projects in Guangdong Province(No.2019CX01C079).

摘　　要：Carbonylation reactions are a valuable synthetic method to construct carbonyl compounds and carbonylation reactions of aryl halides stand out as a highly significant tool for generating carbonyl substituted arenes.However,the important reactions have never been realized in aromatic metallacycles.Herein,we present the first carbonylation reactions of metallaaromatics,specifically alkoxycarbonylation and aminocarbonylation reactions of an osmapentalyne.During the carbonylation process,the electronic and steric properties of nucleophiles are regarded as critical factors.The alcohols with bulky substituents(isopropanol)require more reaction time and tert-butyl alcohol is inert in the reaction.Comparatively,amines,being stronger nucleophiles,exhibit divergent behaviors.Bulky amines undergo aminocarbonylation,whereas small amines prefer direct nucleophilic additions.Control experiments revealed that the intermediate derived from coupling of metal carbyne with CO plays a significant role in the carbonylation reaction.According to these observations,a divergent pathway for the reaction is proposed.Furthermore,the photophysical properties of these carbonyl-functionalized osmapentalene complexes are studied,and the maximum absorption peak of compound with a carboxylic group exhibits a significant red-shift due to the smaller HOMO-LUMO gap.These findings contribute to expanding the reactivity of metallaaromatics and offer new opportunities for the synthesis of carbonyl-functionalized metallacycles.

关 键 词：Carbonylation reactions Metal carbyne AROMATICITY Carbon monoxide METALLACYCLE 

分 类 号：O62[理学—有机化学]