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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- 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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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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