Unusual cyanide and methyl binding modes at a dicobalt macrocycle following acetonitrile C–C bond activation

This communication describes the C-C bond activation of acetonitrile and the trapping of the methyl and cyanide fragments by macrocyclic, dicobalt complexes. Both products display unique structural features as a result of the constraints imposed by the macrocycle. The bridged species [( 3 PDI 2 )Co 2 (μ-CN)(PMe 3 ) 2 ][OTf] ([Co 2 CN] + ) exhibits atypical Co-CN-Co binding, and upon either phosphine dissociation or oxidation, the flexible ligand framework is able to switch between different binding modes of μ-cyanide. Further, the bridging methyl species [( 3 PDI 2 )Co 2 (μ-CH 3 )(PMe 3 )][OTf] ([Co 2 CH 3 ] + ) is the first structurally characterized dicobalt complex with a bridging methyl group.