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

doi:10.1007/430_2020_77

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

Chemistry

Research output: Chapter in Book/Report/Conference proceeding › Chapter

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)][BAr^F ₄] (where Ar^F = 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 language	English
Title of host publication	Structure and Bonding
Publisher	Springer
Pages	183-228
Number of pages	46
DOIs	https://doi.org/10.1007/430_2020_77
Publication status	Published - 3 Nov 2020

Publication series

Name	Structure and Bonding
Volume	186
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 (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.

Publisher Copyright:
© Springer Nature Switzerland AG 2020.

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

Keywords

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

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10.1007/430_2020_77

Algarra et al 2020
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https://link.springer.com/chapter/10.1007%2F430_2020_77

Cite this

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

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)][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.",

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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 (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. Publisher Copyright: {\textcopyright} Springer Nature Switzerland AG 2020. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.",

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AU - Algarra, Andrés G.

AU - Burnage, Arron L.

AU - Iannuzzi, Marcella

AU - Krämer, Tobias

AU - Macgregor, Stuart A.

AU - Pirie, Rachael E.M.

AU - Tegner, Bengt

AU - Weller, Andrew S.

N1 - 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 (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. Publisher Copyright: © Springer Nature Switzerland AG 2020. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2020/11/3

Y1 - 2020/11/3

N2 - 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.

AB - 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.

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BT - Structure and Bonding

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ER -

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

Abstract

Publication series

Bibliographical note

Keywords

Access to Document

Other files and links

Putting Low Coordination into Practice by the Exploration of Metal-sigma-Interactions: Fundamentals, New Catalysts and Catalysis for New Materials

Cite this

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

Abstract

Publication series

Bibliographical note

Keywords

Access to Document

Other files and links

Projects

Putting Low Coordination into Practice by the Exploration of Metal-sigma-Interactions: Fundamentals, New Catalysts and Catalysis for New Materials

Cite this