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21st Century Challenges in Chemical Crystallography II pp 183–228Cite as

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

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Part of the book series: Structure and Bonding ((STRUCTURE,volume 186))

Abstract

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)][BArF4] (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.

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Abbreviations

ArCl:

3,5-C6H3(Cl)2

ArF:

3,5-C6H3(CF3)2

BCP:

Bond critical point

BMO:

Bonding molecular orbital

BP86:

Becke-Perdew 1986

CI-NEB:

Climbing image-nudged elastic band

COA:

Cyclooctane

COD:

Cycloocta-1,5-diene

CV:

Collective variable

Cy:

Cyclohexyl

Cyp:

Cyclopentyl

DFT:

Density functional theory

DZVP:

Double-zeta valence polarisation

FES:

Free energy surface

GIPAW :

Gauge including projector augmented waves

GTH:

Goedecker-Teter-Hutter pseudopotentials

HETCOR:

Heteronuclear correlation

iBu:

Isobutyl

iPr:

Isopropyl

MOLOPT:

Basis sets optimised for molecular calculations

NBA:

Norbornane

NBD:

Norbornadiene

NBO:

Natural bond orbital

NCI:

Non-covalent interaction

PBE:

Perdew-Burke-Ernzenhof

QTAIM:

Quantum theory of atoms in molecules

RCP:

Ring critical point

SC–SC:

Single-crystal-to-single-crystal

SDD:

Stuttgart-Dresden pseudopotentials

SMOM:

Solid-state molecular organometallic

SMOM-Cat:

Solid-state molecular organometallic catalysis

SR:

Shorter range

SSNMR:

Solid-state nuclear magnetic resonance

σ-CAM:

Sigma complex-assisted metathesis

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Acknowledgements

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 (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). 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.

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Authors and Affiliations

  1. Institute of Chemical Sciences, Heriot-Watt University, Edinburgh, UK

    Andrés G. Algarra, Arron L. Burnage, Tobias Krämer, Stuart A. Macgregor, Rachael E. M. Pirie & Bengt Tegner

  2. Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica, Facultad de Ciencias, Instituto de Biomoléculas, Universidad de Cádiz, Cádiz, Spain

    Andrés G. Algarra

  3. Physical-Chemistry Institute, University of Zürich, Zürich, Switzerland

    Marcella Iannuzzi

  4. Department of Chemistry, Maynooth University, Maynooth, Kildare, Ireland

    Tobias Krämer

  5. Department of Chemistry, University of York, York, UK

    Andrew S. Weller

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  1. Andrés G. Algarra
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  2. Arron L. Burnage
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Correspondence to Stuart A. Macgregor .

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Editors and Affiliations

  1. Inorganic Chemistry Laboratory, University of Oxford, Oxford, UK

    D. Michael P. Mingos

  2. Department of Chemistry, University of Bath, Bath, UK

    Paul R. Raithby

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Algarra, A.G. et al. (2020). Computational Studies of the Solid-State Molecular Organometallic (SMOM) Chemistry of Rh s-Alkane Complexes. In: Mingos, D., Raithby, P.R. (eds) 21st Century Challenges in Chemical Crystallography II. Structure and Bonding, vol 186. Springer, Cham. https://doi.org/10.1007/430_2020_77

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