A Structurally Characterized Cobalt(I) σ-Alkane Complex

Timothy M Boyd; Bengt E Tegner; Graham J Tizzard; Antonio J Martínez-Martínez; Samuel E Neale; Michael A Hayward; Simon J Coles; Stuart A Macgregor; Andrew S Weller

doi:10.1002/anie.201914940

A Structurally Characterized Cobalt(I) σ-Alkane Complex

Angew Chem Int Ed Engl. 2020 Apr 6;59(15):6177-6181. doi: 10.1002/anie.201914940. Epub 2020 Feb 20.

Authors

Affiliations

¹ Chemistry Research Laboratories, Department of Chemistry, University of Oxford, Oxford, OX1 3TA, UK.
² Department of Chemistry, University of York, York, YO10 5DD, UK.
³ Institute of Chemical Sciences, Heriot-Watt University, Edinburgh, EH14 4AS, UK.
⁴ UK National Crystallography Service, Chemistry, Faculty of Engineering and Physical Sciences, University of Southampton, Southampton, SO17 1BJ, UK.

Abstract

A cobalt σ-alkane complex, [Co(Cy₂ P(CH₂ )₄ PCy₂ )(norbornane)][BAr^F ₄ ], 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.

Keywords: X-ray diffraction; alkane complexes; cobalt; periodic density functional theory; single crystals.

Abstract

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