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^*

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article › peer-review

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	12 Jan 2021
DOIs	https://doi.org/10.1002/chem.202004585
Publication status	Published - 10 Feb 2021

Keywords

Density functional calculations
Isomerization
Periodic DFT
Rhodium
Selectivity
SMOM

Access to Document

10.1002/chem.202004585Licence: CC BY

Furfari_2021_CAEJ_Selectivity-of-Rh-H-C-binding-sigma-alkane-complex_CC
© 2020 The Authors. This is an open access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0/), which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Final published version, 2.4 MBLicence: CC BY

CCDC 2035752 &2035753: Experimental Crystal Structure Determination
Furfari, S. K. (Creator), Tegner, B. E. (Creator), Burnage, A. L. (Creator), Doyle, L. R. (Creator), Bukvic, A. J. (Creator), Macgregor, S. A. (Creator) & Weller, A. S. (Creator), Cambridge Crystallographic Data Centre, 2021
DOI: 10.5517/ccdc.csd.cc26bcfc, https://dx.doi.org/10.5517/ccdc.csd.cc26bcgd
Dataset

Cite this

@article{3918b0b03432445b9e4cfe0b5ba3423a,

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 = "Density functional calculations, Isomerization, Periodic DFT, Rhodium, Selectivity, SMOM",

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: The authors are grateful to SCG Chemicals, the EPSRC (M024210) and the Leverhulme Trust (RPG-2015-447) for funding",

year = "2021",

month = feb,

day = "10",

doi = "10.1002/chem.202004585",

language = "English",

volume = "27",

pages = "3177--3183",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley & Sons, Ltd",

number = "9",

}

TY - JOUR

T1 - Selectivity of Rh⋅⋅⋅H−C binding in a σ-alkane complex controlled by the secondary microenvironment in the solid state

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: The authors are grateful to SCG Chemicals, the EPSRC (M024210) and the Leverhulme Trust (RPG-2015-447) for funding

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 - Density functional calculations

KW - Isomerization

KW - Periodic DFT

KW - Rhodium

KW - Selectivity

KW - SMOM

U2 - 10.1002/chem.202004585

DO - 10.1002/chem.202004585

M3 - Article

C2 - 33112000

AN - SCOPUS:85099307643

SN - 0947-6539

VL - 27

SP - 3177

EP - 3183

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 9

ER -

Selectivity of Rh⋅⋅⋅H−C binding in a σ-alkane complex controlled by the secondary microenvironment in the solid state

Abstract

Keywords

Access to Document

Fingerprint

Datasets

CCDC 2035752 &2035753: Experimental Crystal Structure Determination

Cite this