A Structurally Characterized Cobalt(I) σ–Alkane Complex

T. M. Boyd, B. Tegner, G. Tizzard, A. Martinez-Martinez, S. E. Neale, M. Hayward, S. Coles, S. A. Macgregor, A. S. Weller
Angewandte Chemie int. Ed.
59 (15), 6177-6181
Published while none of the authors were employed at the CMM


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 η11‐alkane binding mode.