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论文类型：期刊论文

发表时间：2014-06-23

发表刊物：ORGANOMETALLICS

收录刊物：Scopus、EI、SCIE

卷号：33

期号：12

页面范围：2984-2989

ISSN号：0276-7333

摘要：DFT calculations on the Ag-catalyzed carboxylation of phenyl acetylene with CO2 indicate that the true catalytically active species is a CsCO3--coordinated Ag complex rather than neutral PhC  CAg conventionally considered for such a process. The energy barrier for the insertion of CO2 into the C Ag bond of PhC  CAg (28.8 kcal/mol) is higher than that of PhC  CAgI- and PhC  CAgCsCO3- anions (19.0 and 23.6 kcal/mol, respectively). Such an anion as a key intermediate is the predominant feature of the carboxylation process. The electronic effect plays a crucial role in stabilizing such transition states. In addition, the presence of an organic ligand slightly hampers generation of the active species and, therefore, reduced the yield of the final carboxylation product, which was observed experimentally.