Characterizing pressure-induced uranium C-H agostic bonds

Polly L. Arnold; Alessandro Prescimone; Joy H. Farnaby; Stephen M Mansell; Simon Parsons; Nikolas Kaltsoyannis

doi:10.1002/anie.201411250

Characterizing pressure-induced uranium C-H agostic bonds

Polly L. Arnold^*, Alessandro Prescimone, Joy H. Farnaby, Stephen M Mansell, Simon Parsons, Nikolas Kaltsoyannis

^*Corresponding author for this work

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

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Abstract

The diuranium(III) compound [UN′′<inf>2</inf>]<inf>2</inf>(μ-η<sup>6</sup>:η<sup>6</sup>-C<inf>6</inf>H<inf>6</inf>) (N′′=N(SiMe<inf>3</inf>)<inf>2</inf>) has been studied using variable, high-pressure single-crystal X-ray crystallography, and density functional theory . In this compound, the low-coordinate metal cations are coupled through π- and δ-symmetric arene overlap and show close metal-CH contacts with the flexible methyl CH groups of the sterically encumbered amido ligands. The metal-metal separation decreases with increasing pressure, but the most significant structural changes are to the close contacts between ligand CH bonds and the U centers. Although the interatomic distances are suggestive of agostic-type interactions between the U and ligand peripheral CH groups, QTAIM (quantum theory of atoms-in-molecules) computational analysis suggests that there is no such interaction at ambient pressure. However, QTAIM and NBO analyses indicate that the interaction becomes agostic at 3.2 GPa.

Original language	English
Pages (from-to)	6735-6739
Journal	Angewandte Chemie International Edition
Volume	54
Issue number	23
Early online date	16 Apr 2015
DOIs	https://doi.org/10.1002/anie.201411250
Publication status	Published - 1 Jun 2015

Keywords

Actinides
Density functional calculations
High-pressure chemistry
Uranium
X-ray diffraction

ASJC Scopus subject areas

General Chemistry
Catalysis

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10.1002/anie.201411250

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© 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
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title = "Characterizing pressure-induced uranium C-H agostic bonds",

abstract = "The diuranium(III) compound [UN′′2]2(μ-η6:η6-C6H6) (N′′=N(SiMe3)2) has been studied using variable, high-pressure single-crystal X-ray crystallography, and density functional theory . In this compound, the low-coordinate metal cations are coupled through π- and δ-symmetric arene overlap and show close metal-CH contacts with the flexible methyl CH groups of the sterically encumbered amido ligands. The metal-metal separation decreases with increasing pressure, but the most significant structural changes are to the close contacts between ligand CH bonds and the U centers. Although the interatomic distances are suggestive of agostic-type interactions between the U and ligand peripheral CH groups, QTAIM (quantum theory of atoms-in-molecules) computational analysis suggests that there is no such interaction at ambient pressure. However, QTAIM and NBO analyses indicate that the interaction becomes agostic at 3.2 GPa.",

keywords = "Actinides, Density functional calculations, High-pressure chemistry, Uranium, X-ray diffraction",

author = "Arnold, {Polly L.} and Alessandro Prescimone and Farnaby, {Joy H.} and Mansell, {Stephen M} and Simon Parsons and Nikolas Kaltsoyannis",

note = "{"}PLA thanks the Technische Universit{\"a}t M{\"u}nchen – Institute for Advanced Study, funded by the German Excellence Initiative, and the EPSRC. NK thanks University College London for computing resources via the Research Computing “Legion” cluster Legion@UCL and associated services. We thank Diamond Light Source for access to beamline I19 (MT9205).{"}",

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T1 - Characterizing pressure-induced uranium C-H agostic bonds

AU - Arnold, Polly L.

AU - Prescimone, Alessandro

AU - Farnaby, Joy H.

AU - Mansell, Stephen M

AU - Parsons, Simon

AU - Kaltsoyannis, Nikolas

N1 - "PLA thanks the Technische Universität München – Institute for Advanced Study, funded by the German Excellence Initiative, and the EPSRC. NK thanks University College London for computing resources via the Research Computing “Legion” cluster Legion@UCL and associated services. We thank Diamond Light Source for access to beamline I19 (MT9205)."

PY - 2015/6/1

Y1 - 2015/6/1

N2 - The diuranium(III) compound [UN′′2]2(μ-η6:η6-C6H6) (N′′=N(SiMe3)2) has been studied using variable, high-pressure single-crystal X-ray crystallography, and density functional theory . In this compound, the low-coordinate metal cations are coupled through π- and δ-symmetric arene overlap and show close metal-CH contacts with the flexible methyl CH groups of the sterically encumbered amido ligands. The metal-metal separation decreases with increasing pressure, but the most significant structural changes are to the close contacts between ligand CH bonds and the U centers. Although the interatomic distances are suggestive of agostic-type interactions between the U and ligand peripheral CH groups, QTAIM (quantum theory of atoms-in-molecules) computational analysis suggests that there is no such interaction at ambient pressure. However, QTAIM and NBO analyses indicate that the interaction becomes agostic at 3.2 GPa.

AB - The diuranium(III) compound [UN′′2]2(μ-η6:η6-C6H6) (N′′=N(SiMe3)2) has been studied using variable, high-pressure single-crystal X-ray crystallography, and density functional theory . In this compound, the low-coordinate metal cations are coupled through π- and δ-symmetric arene overlap and show close metal-CH contacts with the flexible methyl CH groups of the sterically encumbered amido ligands. The metal-metal separation decreases with increasing pressure, but the most significant structural changes are to the close contacts between ligand CH bonds and the U centers. Although the interatomic distances are suggestive of agostic-type interactions between the U and ligand peripheral CH groups, QTAIM (quantum theory of atoms-in-molecules) computational analysis suggests that there is no such interaction at ambient pressure. However, QTAIM and NBO analyses indicate that the interaction becomes agostic at 3.2 GPa.

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Characterizing pressure-induced uranium C-H agostic bonds

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Stephen M. Mansell

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Characterizing pressure-induced uranium C-H agostic bonds

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Stephen M. Mansell

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