A Structurally Characterized Cobalt(I) σ-Alkane Complex

Abstract

A cobalt σ-alkane complex, [Co(Cy2P(CH2)4PCy2)(norbornane)][BArF4], was synthesized by a single-crystal to single-crystal solid/gas hydrogenation from a norbornadiene precursor, and its structure was determined by X-ray crystallography. Magnetic data show this complex to be a triplet. Periodic DFT and electronic structure analyses revealed weak C−H→Co σ-interactions, augmented by dispersive stabilization between the alkane ligand and the anion microenvironment. The calculations are most consistent with a η1:η1-alkane binding mode.