Solution, solid-state, and computational analysis of agostic interactions in a coherent set of low-coordinate rhodium(III) and iridium(III) complexes
Solution, solid-state, and computational analysis of agostic interactions in a coherent set of low-coordinate rhodium(III) and iridium(III) complexes
A homologous family of low-coordinate complexes of the formulation trans-[M(2,2′-biphenyl)(PR3)2][BArF4] (M=Rh, Ir; R=Ph, Cy, iPr, iBu) has been prepared and extensively structurally characterised. Enabled through a comprehensive set of solution phase (VT 1H and 31P NMR spectroscopy) and solid-state (single crystal X-ray diffraction) data, and analysis in silico (DFT-based NBO and QTAIM analysis), the structural features of the constituent agostic interactions have been systematically interrogated. The combined data substantiates the adoption of stronger agostic interactions for the IrIII compared to RhIII complexes and, with respect to the phosphine ligands, in the order PiBu3>PCy3>PiPr3>PPh3. In addition to these structure–property relationships, the effect of crystal packing on the agostic interactions was investigated in the tricyclohexylphosphine complexes. Compression of the associated cations, through inclusion of a more bulky solvent molecule (1,2-difluorobenzene vs. CH2Cl2) in the lattice or collection of data at very low temperature (25 vs. 150 K), lead to small but statistically significant shortening of the M−H−C distances.
X-ray diffraction, agostic interactions, crystal engineering, ligand effects, organometallic chemistry
4927-4938
Knighton, Richard C.
5a63128e-0ebd-466a-b327-3aee6e85a76d
Emerson-King, Jack
6ee84728-72a7-496a-a05c-48720dea9d48
Rourke, Jonathan P.
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Ohlin, C. André
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Chaplin, Adrian B.
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3 April 2018
Knighton, Richard C.
5a63128e-0ebd-466a-b327-3aee6e85a76d
Emerson-King, Jack
6ee84728-72a7-496a-a05c-48720dea9d48
Rourke, Jonathan P.
78f0b8ec-5004-4327-b14b-f58a673f3ab6
Ohlin, C. André
c452d8a9-8381-4a6c-8de7-c3710121ee5b
Chaplin, Adrian B.
6af87db8-8153-44ea-88ef-e25eb2cd5f9d
Knighton, Richard C., Emerson-King, Jack, Rourke, Jonathan P., Ohlin, C. André and Chaplin, Adrian B.
(2018)
Solution, solid-state, and computational analysis of agostic interactions in a coherent set of low-coordinate rhodium(III) and iridium(III) complexes.
Chemistry - A European Journal, 24 (19), .
(doi:10.1002/chem.201705990).
Abstract
A homologous family of low-coordinate complexes of the formulation trans-[M(2,2′-biphenyl)(PR3)2][BArF4] (M=Rh, Ir; R=Ph, Cy, iPr, iBu) has been prepared and extensively structurally characterised. Enabled through a comprehensive set of solution phase (VT 1H and 31P NMR spectroscopy) and solid-state (single crystal X-ray diffraction) data, and analysis in silico (DFT-based NBO and QTAIM analysis), the structural features of the constituent agostic interactions have been systematically interrogated. The combined data substantiates the adoption of stronger agostic interactions for the IrIII compared to RhIII complexes and, with respect to the phosphine ligands, in the order PiBu3>PCy3>PiPr3>PPh3. In addition to these structure–property relationships, the effect of crystal packing on the agostic interactions was investigated in the tricyclohexylphosphine complexes. Compression of the associated cations, through inclusion of a more bulky solvent molecule (1,2-difluorobenzene vs. CH2Cl2) in the lattice or collection of data at very low temperature (25 vs. 150 K), lead to small but statistically significant shortening of the M−H−C distances.
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Chemistry A European J - 2018 - Knighton
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e-pub ahead of print date: 28 February 2018
Published date: 3 April 2018
Keywords:
X-ray diffraction, agostic interactions, crystal engineering, ligand effects, organometallic chemistry
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Local EPrints ID: 482115
URI: http://eprints.soton.ac.uk/id/eprint/482115
ISSN: 0947-6539
PURE UUID: 97209576-52cc-4713-ba65-9ecf0b65a95a
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Date deposited: 19 Sep 2023 16:54
Last modified: 18 Mar 2024 04:15
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Author:
Richard C. Knighton
Author:
Jack Emerson-King
Author:
Jonathan P. Rourke
Author:
C. André Ohlin
Author:
Adrian B. Chaplin
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