A Series of Crystallographically Characterized Linear and Branched sigma-Alkane Complexes of Rhodium: From Propane to 3-Methylpentane
Alexander J Bukvic, Arron L Burnage, Graham J Tizzard, Antonio J Martinez-Martinez, Alasdair McKay, Nicholas H Rees, Bengt E Tegner, Tobias Kramer, Heather Fish, Mark R Warren, Simon J Coles, Stuart A Macgregor, Andrew S Weller
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | AMER CHEMICAL SOC | Published : 2021
Using solid-state molecular organometallic (SMOM) techniques, in particular solid/gas single-crystal to single-crystal reactivity, a series of σ-alkane complexes of the general formula [Rh(Cy2PCH2CH2PCy2)(ηn:ηm-alkane)][BArF4] have been prepared (alkane = propane, 2-methylbutane, hexane, 3-methylpentane; ArF = 3,5-(CF3)2C6H3). These new complexes have been characterized using single crystal X-ray diffraction, solid-state NMR spectroscopy and DFT computational techniques and present a variety of Rh(I)···H-C binding motifs at the metal coordination site: 1,2-η2:η2 (2-methylbutane), 1,3-η2:η2 (propane), 2,4-η2:η2 (hexane), and 1,4-η1:η2 (3-methylpentane). For the linear alkanes propane and hexa..View full abstract
Awarded by EPSRC
Awarded by Leverhulme Trust
This paper is dedicated to Professor Robin N. Perutz on the occasion of his 70th birthday. We thank the EPSRC (EP/M024210, and the UK National Crystallography Service), the Leverhulme Trust (RPG-2015-447), and SGC Chemicals for funding, T. M. Boyd (York) for experimental assistance and useful discussions, and Dr. M. Chadwick (Imperial College) for the initial synthesis of [1-isoprene][BArF4]. This work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk) and the Cirrus UK National Tier-2 HPC Service at the EPCC (http://www.cirrus.ac.uk) funded by the University of Edinburgh and the EPSRC (EP/P020267/1).