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Published on: April 19, 2019
Unusual cyanide and methyl binding modes at a dicobalt macrocycle following acetonitrile C-C bond activation
Ariana Z Spentzos1, Michael R Gau, Patrick J Carroll
1P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, USA. tomson@upenn.edu.
Abstract:
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 [(3PDI2)Co2(μ-CN)(PMe3)2][OTf] ([Co2CN]+) 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 [(3PDI2)Co2(μ-CH3)(PMe3)][OTf] ([Co2CH3]+) is the first structurally characterized dicobalt complex with a bridging methyl group.
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