MicroED Characterization of a Robust Cationic -Alkane Complex Stabilized by the [B(3,5-(SF5)2C6H3)4]– Anion, via On-Grid Solid/Gas Single-Crystal to Single-Crystal Reactivity

Andrew Weller; Laurence Robertson Doyle; Emily Thompson; Arron L. Burnage; Adrian C. Whitwood; Huw Thomas Jenkins; Stuart A. Macgregor

doi:10.1039/D2DT00335J

MicroED Characterization of a Robust Cationic -Alkane Complex Stabilized by the [B(3,5-(SF5)2C6H3)4]– Anion, via On-Grid Solid/Gas Single-Crystal to Single-Crystal Reactivity

Andrew Weller, Laurence Robertson Doyle, Emily Thompson, Arron L. Burnage, Adrian C. Whitwood, Huw Thomas Jenkins, Stuart A. Macgregor

Chemistry

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

Abstract

Microcrystalline (~1 m) [Rh(Cy2PCH2CH2PCy2)(norbornadiene)][S-BArF4], [S-BArF4] = [B(3,5-(SF5)2C6H3)4]–, reacts with H2 in a single-crystal to single-crystal transformation to form the -alkane complex [Rh(Cy2PCH2CH2PCy2)(norbornane)][S-BArF4], for which the structure was determined by microcrystal Electron Diffraction (microED), to 0.95 Å resolution, via an on-grid hydrogenation, and a complementary single-crystal X-ray diffraction study on larger, but challenging to isolate, crystals. Comparison with the [BArF4]– analogue [ArF = 3,5-(CF3)2C5H3)] shows that the [S-BArF4]– anion makes the -alkane complex robust towards decomposition both thermally and when suspended in pentane. Subsequent reactivity with dissolved ethene in a pentane slurry, forms [Rh(Cy2PCH2CH2PCy2)(ethene)2][S-BArF4], and the catalytic dimerisation/isomerisation of ethene to 2-butenes. The increased stability of [S-BArF4]– salts is identified as being due to increased non-covalent interactions in the lattice, resulting in a solid-state molecular organometallic material with desirable stability characteristics.

Original language	English
Journal	Dalton Transactions
Early online date	3 Feb 2022
DOIs	https://doi.org/10.1039/D2DT00335J
Publication status	E-pub ahead of print - 3 Feb 2022

Bibliographical note

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10.1039/D2DT00335JLicence: CC BY

Supporting_InformationFinal published version, 9.16 MBLicence: CC BY
d2dt00335j
© The Royal Society of Chemistry 2022
Final published version, 1.7 MBLicence: CC BY

Putting Low Coordination into Practice by the Exploration of Metal-sigma-Interactions: Fundamentals, New Catalysts and Catalysis for New Materials
Weller, A. (Principal investigator)
EPSRC
1/01/20 → 31/03/22
Project: Research project (funded) › Research
A regional cryo-EM Facility at the University of York
Davies, G. J. (Principal investigator), Antson, A. A. (Co-investigator), Brzozowski, A. M. (Co-investigator), Cowtan, K. (Co-investigator), Mottram, J. C. (Co-investigator), Plevin, M. J. (Co-investigator) & Potts, J. R. (Co-investigator)
20/12/18 → 19/12/23
Project: Research project (funded) › Research

MicroED Characterization of a Robust Cationic σ-Alkane Complex Stabilized by the [B(3,5-(SF5)2C6H3)4]– Anion, via On-Grid Solid/Gas Single-Crystal to Single-Crystal Reactivity.
Doyle, L. R. (Creator), Thompson, E. A. (Creator), Burnage, A. L. (Creator), Whitwood, A. C. (Creator), Jenkins, H. T. (Creator), Macgregor, S. A. (Creator) & Weller, A. S. (Creator), Zenodo, 3 Feb 2022
DOI: 10.5281/zenodo.5760938
Dataset

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Weller, A., Doyle, L. R., Thompson, E., Burnage, A. L., Whitwood, A. C., Jenkins, H. T., & Macgregor, S. A. (2022). MicroED Characterization of a Robust Cationic -Alkane Complex Stabilized by the [B(3,5-(SF5)2C6H3)4]– Anion, via On-Grid Solid/Gas Single-Crystal to Single-Crystal Reactivity. Dalton Transactions. Advance online publication. https://doi.org/10.1039/D2DT00335J

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title = "MicroED Characterization of a Robust Cationic -Alkane Complex Stabilized by the [B(3,5-(SF5)2C6H3)4]– Anion, via On-Grid Solid/Gas Single-Crystal to Single-Crystal Reactivity",

abstract = "Microcrystalline (~1 m) [Rh(Cy2PCH2CH2PCy2)(norbornadiene)][S-BArF4], [S-BArF4] = [B(3,5-(SF5)2C6H3)4]–, reacts with H2 in a single-crystal to single-crystal transformation to form the -alkane complex [Rh(Cy2PCH2CH2PCy2)(norbornane)][S-BArF4], for which the structure was determined by microcrystal Electron Diffraction (microED), to 0.95 {\AA} resolution, via an on-grid hydrogenation, and a complementary single-crystal X-ray diffraction study on larger, but challenging to isolate, crystals. Comparison with the [BArF4]– analogue [ArF = 3,5-(CF3)2C5H3)] shows that the [S-BArF4]– anion makes the -alkane complex robust towards decomposition both thermally and when suspended in pentane. Subsequent reactivity with dissolved ethene in a pentane slurry, forms [Rh(Cy2PCH2CH2PCy2)(ethene)2][S-BArF4], and the catalytic dimerisation/isomerisation of ethene to 2-butenes. The increased stability of [S-BArF4]– salts is identified as being due to increased non-covalent interactions in the lattice, resulting in a solid-state molecular organometallic material with desirable stability characteristics. ",

author = "Andrew Weller and Doyle, {Laurence Robertson} and Emily Thompson and Burnage, {Arron L.} and Whitwood, {Adrian C.} and Jenkins, {Huw Thomas} and Macgregor, {Stuart A.}",

note = "{\textcopyright} The Royal Society of Chemistry 2022 ",

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T1 - MicroED Characterization of a Robust Cationic -Alkane Complex Stabilized by the [B(3,5-(SF5)2C6H3)4]– Anion, via On-Grid Solid/Gas Single-Crystal to Single-Crystal Reactivity

AU - Weller, Andrew

AU - Doyle, Laurence Robertson

AU - Thompson, Emily

AU - Burnage, Arron L.

AU - Whitwood, Adrian C.

AU - Jenkins, Huw Thomas

AU - Macgregor, Stuart A.

PY - 2022/2/3

Y1 - 2022/2/3

N2 - Microcrystalline (~1 m) [Rh(Cy2PCH2CH2PCy2)(norbornadiene)][S-BArF4], [S-BArF4] = [B(3,5-(SF5)2C6H3)4]–, reacts with H2 in a single-crystal to single-crystal transformation to form the -alkane complex [Rh(Cy2PCH2CH2PCy2)(norbornane)][S-BArF4], for which the structure was determined by microcrystal Electron Diffraction (microED), to 0.95 Å resolution, via an on-grid hydrogenation, and a complementary single-crystal X-ray diffraction study on larger, but challenging to isolate, crystals. Comparison with the [BArF4]– analogue [ArF = 3,5-(CF3)2C5H3)] shows that the [S-BArF4]– anion makes the -alkane complex robust towards decomposition both thermally and when suspended in pentane. Subsequent reactivity with dissolved ethene in a pentane slurry, forms [Rh(Cy2PCH2CH2PCy2)(ethene)2][S-BArF4], and the catalytic dimerisation/isomerisation of ethene to 2-butenes. The increased stability of [S-BArF4]– salts is identified as being due to increased non-covalent interactions in the lattice, resulting in a solid-state molecular organometallic material with desirable stability characteristics.

AB - Microcrystalline (~1 m) [Rh(Cy2PCH2CH2PCy2)(norbornadiene)][S-BArF4], [S-BArF4] = [B(3,5-(SF5)2C6H3)4]–, reacts with H2 in a single-crystal to single-crystal transformation to form the -alkane complex [Rh(Cy2PCH2CH2PCy2)(norbornane)][S-BArF4], for which the structure was determined by microcrystal Electron Diffraction (microED), to 0.95 Å resolution, via an on-grid hydrogenation, and a complementary single-crystal X-ray diffraction study on larger, but challenging to isolate, crystals. Comparison with the [BArF4]– analogue [ArF = 3,5-(CF3)2C5H3)] shows that the [S-BArF4]– anion makes the -alkane complex robust towards decomposition both thermally and when suspended in pentane. Subsequent reactivity with dissolved ethene in a pentane slurry, forms [Rh(Cy2PCH2CH2PCy2)(ethene)2][S-BArF4], and the catalytic dimerisation/isomerisation of ethene to 2-butenes. The increased stability of [S-BArF4]– salts is identified as being due to increased non-covalent interactions in the lattice, resulting in a solid-state molecular organometallic material with desirable stability characteristics.

U2 - 10.1039/D2DT00335J

DO - 10.1039/D2DT00335J

M3 - Article

SN - 1477-9234

JO - Dalton Transactions

JF - Dalton Transactions

ER -

MicroED Characterization of a Robust Cationic -Alkane Complex Stabilized by the [B(3,5-(SF5)2C6H3)4]– Anion, via On-Grid Solid/Gas Single-Crystal to Single-Crystal Reactivity

Abstract

Bibliographical note

Access to Document

Projects

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

A regional cryo-EM Facility at the University of York

Datasets

MicroED Characterization of a Robust Cationic σ-Alkane Complex Stabilized by the [B(3,5-(SF5)2C6H3)4]– Anion, via On-Grid Solid/Gas Single-Crystal to Single-Crystal Reactivity.

Cite this