DFT Studies An Unusual Carboxylation Mechanism of the C-H Bond of Terminal Alkynes by Silver Complexes
作者单位：大连理工大学精细化工国家重点实验室
会议名称：《第十八届全国金属有机化学学术研讨会》
会议日期：2014年
学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学]
基 金：国家自然科学基金(21174023,21028001) 中央高校基本科研业务费专项资金(DUT13ZD103)资助项目
摘 要：DFT calculations on the Ag-catalyzed carboxylation of phenyl acetylene with CO indicate that the true catalytically active species is a CsCO-coordinated Ag complex rather than neutral PhC≡CAg conventionally considered for such a *** energy barrier for the insertion of COinto the C-Ag bond of PhC≡CAg(28.8 kcal/mol)is higher than that of PhC≡CAgIand PhC≡CAgCsCOanions(19.0 and 23.6 kcal/mol,respectively).Such an anion as a key