A Structurally Characterized Cobalt(I) σ–Alkane Complex

A cobalt σ‐alkane complex, [Co(Cy₂P(CH₂)₄PCy₂)(norbornane)][BAr^F₄], 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.