Gold Phosphole Complexes as Efficient Catalysts for Alkyne Activation

Gold­(I) complexes bearing monophosphole ligands were synthesized, and their electronic and steric properties were compared to those of their triphenylphosphine-based counterparts. Cationic phosphole-based gold­(I) complexes are active and selective in enyne cycloisomerization and in olefin cyclopropanation, with a good correlation between the ligand σ-donor ability and the catalytic activity. For the most efficient ligand, 1-phenyl-2,3,4,5-tetramethylphosphole (TMP), a highly active, selective, and stable cationic [Au­(TMP)­(CH3CN)]­SbF6 complex was isolated.

本研究合成了一系列带有单磷杂环戊二烯配体（monophosphole ligands）的一价金配合物（Gold(I) complexes），并将其电子性质与空间位阻性质与基于三苯基膦（triphenylphosphine）的对应配合物进行了对比。阳离子型磷杂环戊二烯基金配合物在烯炔环异构化（enyne cycloisomerization）与烯烃环丙烷化（olefin cyclopropanation）反应中表现出催化活性与选择性，且配体的σ给电子能力（σ-donor ability）与催化活性之间存在良好的相关性。针对性能最优的配体1-苯基-2,3,4,5-四甲基磷杂环戊二烯（1-phenyl-2,3,4,5-tetramethylphosphole，缩写为TMP），我们成功分离得到了高活性、高选择性且高稳定的阳离子型[Au(TMP)(CH3CN)]SbF6配合物。