Computational Studies of the Solid-State Molecular Organometallic (SMOM) Chemistry of Rh !-Alkane Complexes

Andrés G. Algarra, Arron L. Burnage, Marcella Iannuzzi, Tobias Krämer, Stuart A. Macgregor*, Rachael E.M. Pirie, Bengt Tegner, Andrew S. Weller

*Corresponding author for this work

Research output: Chapter in Book/Report/Conference proceedingChapter


A review of computational studies on the structures, bonding and reactivity of rhodium σ-alkane complexes in the solid state is presented. These complexes of the general form [(R2P(CH2)nPR2)Rh(alkane)][BArF 4] (where ArF = 3,5-(CF3)2C6H3) are formed via solid/gas hydrogenation of alkene precursors, often in single-crystal-to-single-crystal (SC-SC) transformations. Molecular and periodic density functional theory (DFT) calculations complement experimental characterisation techniques (X-ray, solid-state NMR) to provide a detailed picture of the structure and bonding in these species. These σ-alkane complexes exhibit reactivity in the solid state, undergoing fluxional processes, and access different alkane binding modes that link to C-H activation and H/D exchange. The mechanisms of several of these processes have been defined using periodic DFT calculations which provide excellent quantitative agreement with the available experimental activation barriers. A comparison of computed results derived from periodic DFT calculations, where the full solid-state environment is taken into account, with simple model calculations using the isolated molecular cations highlights the importance of modelling the solid state to reproduce the structures of these alkane complexes. The solid-state environment can also have a significant impact on the computed reaction energetics.

Original languageEnglish
Title of host publicationStructure and Bonding
Number of pages46
Publication statusPublished - 3 Nov 2020

Publication series

NameStructure and Bonding
ISSN (Print)0081-5993
ISSN (Electronic)1616-8550

Bibliographical note

Funding Information:
This work was supported by the EPSRC (SAM, ASW: EP/M024210, EP/K035908, EP/K035681) and the Spanish Government (AGA). Calculations used both the ARCHER UK National Supercomputing Service ( and the Cirrus UK National Tier-2 HPC Service at EPCC ( funded by the University of Edinburgh and EPSRC (EP/P020267/1). TK thanks Profs Toon Verstraelen, An Ghysels and Veronique van Speybroek (Center for Molecular Modelling, University of Ghent) for useful discussions and the Royal Society of Chemistry and the Scottish Funding Council (administered by ScotCHEM) for travel grants.

Publisher Copyright:
© Springer Nature Switzerland AG 2020.

Copyright 2021 Elsevier B.V., All rights reserved.


  • C-H activation
  • Catalysis
  • Periodic DFT
  • Rh
  • Single-crystal-to-single-crystal
  • SMOM
  • SMOM-Cat
  • Solid-state molecular organometallic chemistry
  • σ-Alkane complexes

Cite this