Modification of cobalt bis(dicarbollide) ions with nitrile groups on carbon atoms: a unique low-temperature skeletal rearrangement due to the specific electron-donor character of CN substitution†

Abstract

Herein, we report on the synthesis and stereochemistry of mono- and isomeric dinitrile derivatives of [(1,2-C₂B₉H₁₁)₂-3,3′-Co]⁻ ions. The shape and electronic properties of CN groups can apparently surmount the strain associated with the substitution of two vicinal carbon positions. Owing to electron donation to the cage, this results in a substituent-induced rearrangement of one of the carbon atoms to the upper pentagonal ring. The molecular structure of this isomer was confirmed using sc-XRD and DFT chemical computations.