Open AccessUnusual cyanide and methyl binding modes at a dicobalt macrocycle following acetonitrile C–C bond activation
Author(s) -
Ariana Spentzos,
Michael R. Gau,
Patrick J. Carroll,
Neil C. Tomson
Publication year - 2020
Publication title -
chemical communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.837
H-Index - 333
eISSN - 1364-548X
pISSN - 1359-7345
DOI - 10.1039/d0cc03521a
Subject(s) - chemistry , cyanide , phosphine , acetonitrile , dissociation (chemistry) , stereochemistry , ligand (biochemistry) , medicinal chemistry , photochemistry , receptor , catalysis , organic chemistry , biochemistry
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.