Journal article

Room Temperature Acceptorless Alkane Dehydrogenation from Molecular sigma-Alkane Complexes

Alasdair I McKay, Alexander J Bukvic, Bengt E Tegner, Arron L Burnage, Antonio J Martinez-Martinez, Nicholas H Rees, Stuart A Macgregor, Andrew S Weller

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | AMER CHEMICAL SOC | Published : 2019

Abstract

The non-oxidative catalytic dehydrogenation of light alkanes via C-H activation is a highly endothermic process that generally requires high temperatures and/or a sacrificial hydrogen acceptor to overcome unfavorable thermodynamics. This is complicated by alkanes being such poor ligands, meaning that binding at metal centers prior to C-H activation is disfavored. We demonstrate that by biasing the pre-equilibrium of alkane binding, by using solid-state molecular organometallic chemistry (SMOM-chem), well-defined isobutane and cyclohexane σ-complexes, [Rh(Cy2PCH2CH2PCy2)(η:η-(H3C)CH(CH3)2][BArF4] and [Rh(Cy2PCH2CH2PCy2)(η:η-C6H12)][BArF4] can be prepared by simple hydrogenation in a solid/gas..

View full abstract

University of Melbourne Researchers

Grants

Awarded by EPSRC


Awarded by Leverhulme Trust


Funding Acknowledgements

We thank the EPSRC (EP/M024210, EP/K035908, EP/K035681), the Leverhulme Trust (RPG-2015-447) and SCG Chemicals Co., Ltd, Thailand for funding. This work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk) and the Cirrus UK National Tier-2 HPC Service at EPCC (http://www.cirrus.ac.uk) funded by the University of Edinburgh and EPSRC (EP/P020267/1). We thank Dr. Graham Tizzard (UK National Crystallographic Service) for data collection on [1-C<INF>6</INF>H<INF>8</INF>][BAr<INF>4</INF><SUP>F</SUP>], and Dr. Hamish Yeung for valuable discussions on solid-state kinetics.