Selectivity of Rh···H-C Binding in a σ-Alkane Complex Controlled by the Secondary Microenvironment in the Solid-State

Samantha K. Furfari; Bengt E. Tegner; Arron L. Burnage; Laurence R. Doyle; Alexander J. Bukvic; Stuart A. Macgregor; Andrew S. Weller

doi:10.1002/chem.202004585

Selectivity of Rh···H-C Binding in a σ-Alkane Complex Controlled by the Secondary Microenvironment in the Solid-State

Samantha K. Furfari, Bengt E. Tegner, Arron L. Burnage, Laurence R. Doyle, Alexander J. Bukvic, Stuart A. Macgregor, Andrew S. Weller

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Abstract

Single‐crystal to single‐crystal solid‐state molecular organometallic (SMOM) techniques are used for the synthesis and structural characterization of the σ‐alkane complex [Rh(tBu₂PCH₂CH₂CH₂PtBu₂)(η²,η²‐C₇H₁₂)][BAr^F₄] (Ar^F=3,5‐(CF₃)₂C₆H₃), in which the alkane (norbornane) binds through two exo‐C−H⋅⋅⋅Rh interactions. In contrast, the bis‐cyclohexyl phosphine analogue shows endo‐alkane binding. A comparison of the two systems, supported by periodic DFT calculations, NCI plots and Hirshfeld surface analyses, traces this different regioselectivity to subtle changes in the local microenvironment surrounding the alkane ligand. A tertiary periodic structure supporting a secondary microenvironment that controls binding at the metal site has parallels with enzymes. The new σ‐alkane complex is also a catalyst for solid/gas 1‐butene isomerization, and catalyst resting states are identified for this.

Original language	English
Pages (from-to)	3177-3183
Number of pages	7
Journal	Chemistry - A European Journal
Volume	27
Issue number	9
Early online date	28 Oct 2020
DOIs	https://doi.org/10.1002/chem.202004585
Publication status	Published - 10 Feb 2021

Keywords

SMOM
density functional calculations
isomerization
periodic DFT
rhodium
selectivity

ASJC Scopus subject areas

Catalysis
Organic Chemistry

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title = "Selectivity of Rh···H-C Binding in a σ-Alkane Complex Controlled by the Secondary Microenvironment in the Solid-State",

abstract = "Single‐crystal to single‐crystal solid‐state molecular organometallic (SMOM) techniques are used for the synthesis and structural characterization of the σ‐alkane complex [Rh(tBu2PCH2CH2CH2PtBu2)(η2,η2‐C7H12)][BArF4] (ArF=3,5‐(CF3)2C6H3), in which the alkane (norbornane) binds through two exo‐C−H⋅⋅⋅Rh interactions. In contrast, the bis‐cyclohexyl phosphine analogue shows endo‐alkane binding. A comparison of the two systems, supported by periodic DFT calculations, NCI plots and Hirshfeld surface analyses, traces this different regioselectivity to subtle changes in the local microenvironment surrounding the alkane ligand. A tertiary periodic structure supporting a secondary microenvironment that controls binding at the metal site has parallels with enzymes. The new σ‐alkane complex is also a catalyst for solid/gas 1‐butene isomerization, and catalyst resting states are identified for this.",

keywords = "SMOM, density functional calculations, isomerization, periodic DFT, rhodium, selectivity",

author = "Furfari, {Samantha K.} and Tegner, {Bengt E.} and Burnage, {Arron L.} and Doyle, {Laurence R.} and Bukvic, {Alexander J.} and Macgregor, {Stuart A.} and Weller, {Andrew S.}",

note = "Funding Information: We are grateful to SCG Chemicals, the EPSRC (M024210) and the Leverhulme Trust (RPG‐2015‐447) for funding; Professor Neil Champness (University of Nottingham, UK) for useful discussions and alerting us to the use of CrystalExplorer to explore weak interactions in the solid state; and Dr Jos{\'e} Manuel Men{\'e}ndez (Heriot‐Watt) for excellent IT support. Publisher Copyright: {\textcopyright} 2020 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH",

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AU - Furfari, Samantha K.

AU - Tegner, Bengt E.

AU - Burnage, Arron L.

AU - Doyle, Laurence R.

AU - Bukvic, Alexander J.

AU - Macgregor, Stuart A.

AU - Weller, Andrew S.

N1 - Funding Information: We are grateful to SCG Chemicals, the EPSRC (M024210) and the Leverhulme Trust (RPG‐2015‐447) for funding; Professor Neil Champness (University of Nottingham, UK) for useful discussions and alerting us to the use of CrystalExplorer to explore weak interactions in the solid state; and Dr José Manuel Menéndez (Heriot‐Watt) for excellent IT support. Publisher Copyright: © 2020 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH

PY - 2021/2/10

Y1 - 2021/2/10

N2 - Single‐crystal to single‐crystal solid‐state molecular organometallic (SMOM) techniques are used for the synthesis and structural characterization of the σ‐alkane complex [Rh(tBu2PCH2CH2CH2PtBu2)(η2,η2‐C7H12)][BArF4] (ArF=3,5‐(CF3)2C6H3), in which the alkane (norbornane) binds through two exo‐C−H⋅⋅⋅Rh interactions. In contrast, the bis‐cyclohexyl phosphine analogue shows endo‐alkane binding. A comparison of the two systems, supported by periodic DFT calculations, NCI plots and Hirshfeld surface analyses, traces this different regioselectivity to subtle changes in the local microenvironment surrounding the alkane ligand. A tertiary periodic structure supporting a secondary microenvironment that controls binding at the metal site has parallels with enzymes. The new σ‐alkane complex is also a catalyst for solid/gas 1‐butene isomerization, and catalyst resting states are identified for this.

AB - Single‐crystal to single‐crystal solid‐state molecular organometallic (SMOM) techniques are used for the synthesis and structural characterization of the σ‐alkane complex [Rh(tBu2PCH2CH2CH2PtBu2)(η2,η2‐C7H12)][BArF4] (ArF=3,5‐(CF3)2C6H3), in which the alkane (norbornane) binds through two exo‐C−H⋅⋅⋅Rh interactions. In contrast, the bis‐cyclohexyl phosphine analogue shows endo‐alkane binding. A comparison of the two systems, supported by periodic DFT calculations, NCI plots and Hirshfeld surface analyses, traces this different regioselectivity to subtle changes in the local microenvironment surrounding the alkane ligand. A tertiary periodic structure supporting a secondary microenvironment that controls binding at the metal site has parallels with enzymes. The new σ‐alkane complex is also a catalyst for solid/gas 1‐butene isomerization, and catalyst resting states are identified for this.

KW - SMOM

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KW - rhodium

KW - selectivity

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