Ambient Stable Cyanomethylcopper(III) Complex: a Strong Cu-C_sp Bond Supported by a PS3-Tripodal Chelator

An organocuprate(III) complex, [Cu(^TMSPS3)(CH₂CN)]^- (2), was identified along with a sequential derivative, [Cu(^TMSPS3)(CN)]^- (3), and an intermediate, [Cu(^TMSPS3)(HN═PPh₃)] (4), formed in a relative transformation. Apical ligands among these complexes all strongly associate with a robust trigonal copper(III) platform. The nature of the ligand binding was spectroscopically and computationally investigated through a series of copper(III) complexes. The bonding along the principal C₃ axis is adaptable, and σ interaction dominates the axial ligand coordination, where the cyanomethyl group exhibits the strongest bonding. Complex 2 is a scarce example of a thermostable aliphatic organocuprate(III) compound, which sheds some light on the organocopper(III) chemistry widely involved in many copper-mediated catalyses.