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The trans influence in unsymmetrical pincer palladacycles: an experimental and computational study

The trans influence in unsymmetrical pincer palladacycles: an experimental and computational study
The trans influence in unsymmetrical pincer palladacycles: an experimental and computational study
A library of unsymmetrical SCN pincer palladacycles, [ClPd{2-pyr-6-(RSCH2)C6H3}], R = Et, Pr, Ph, p-MePh, and p-MeOPh, pyr = pyridine, has been synthesized via C–H bond activation, and used, along with PCN and N’CN unsymmetrical pincer palladacycles previously synthesized by the authors, to determine the extent to which the trans influence is exhibited in unsymmetrical pincer palladacycles. The trans influence is quantified by analysis of structural changes in the X-ray crystal and density functional theory (DFT) optimized structures and a topological analysis of the
electron density using quantum theory of atoms in molecules (QTAIM) to determine the strength of the Pd-donor atom interaction. It is found that the trans influence is controlled by the nature of the donor atom and although the substituents on the donor-ligand affect the Pd-donor atom interaction through the varied electronic and steric constraints, they do not influence the bonding of the ligand
trans to it. The data indicate that the strength of the trans influence is P > S > N. Furthermore, the synthetic route to the family of SCN pincer palladacycles presented demonstrates the potential of late stage derivitization for the effective synthesis of ligands towards unsymmetrical pincer palladacycles.
1-14
Boonseng, Sarote
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Roffe, Gavin W.
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Jones, Rhiannon N.
001d0de7-edbd-479c-a243-4e3b61115b0e
Tizzard, Graham J.
8474c0fa-40df-43a6-a662-7f3c4722dbf2
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Spencer, John
a3cf55cd-a4c7-4af6-b16c-96c8fb8c4cf4
Cox, Hazel
334ee45b-6c64-4c3b-a3e0-2a72f342f2cf
Boonseng, Sarote
83b6e024-fc9d-4f5f-9dc4-0e7c4c10d34f
Roffe, Gavin W.
77d00ee6-a56e-49ed-af4a-670b5c452ade
Jones, Rhiannon N.
001d0de7-edbd-479c-a243-4e3b61115b0e
Tizzard, Graham J.
8474c0fa-40df-43a6-a662-7f3c4722dbf2
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Spencer, John
a3cf55cd-a4c7-4af6-b16c-96c8fb8c4cf4
Cox, Hazel
334ee45b-6c64-4c3b-a3e0-2a72f342f2cf

Boonseng, Sarote, Roffe, Gavin W., Jones, Rhiannon N., Tizzard, Graham J., Coles, Simon J., Spencer, John and Cox, Hazel (2016) The trans influence in unsymmetrical pincer palladacycles: an experimental and computational study. [in special issue: Traversing the Boundaries of Inorganic Chemistry] Inorganics, 4 (3), 1-14. (doi:10.3390/inorganics4030025).

Record type: Article

Abstract

A library of unsymmetrical SCN pincer palladacycles, [ClPd{2-pyr-6-(RSCH2)C6H3}], R = Et, Pr, Ph, p-MePh, and p-MeOPh, pyr = pyridine, has been synthesized via C–H bond activation, and used, along with PCN and N’CN unsymmetrical pincer palladacycles previously synthesized by the authors, to determine the extent to which the trans influence is exhibited in unsymmetrical pincer palladacycles. The trans influence is quantified by analysis of structural changes in the X-ray crystal and density functional theory (DFT) optimized structures and a topological analysis of the
electron density using quantum theory of atoms in molecules (QTAIM) to determine the strength of the Pd-donor atom interaction. It is found that the trans influence is controlled by the nature of the donor atom and although the substituents on the donor-ligand affect the Pd-donor atom interaction through the varied electronic and steric constraints, they do not influence the bonding of the ligand
trans to it. The data indicate that the strength of the trans influence is P > S > N. Furthermore, the synthetic route to the family of SCN pincer palladacycles presented demonstrates the potential of late stage derivitization for the effective synthesis of ligands towards unsymmetrical pincer palladacycles.

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More information

Accepted/In Press date: 5 August 2016
e-pub ahead of print date: 11 August 2016
Published date: 11 August 2016

Identifiers

Local EPrints ID: 400065
URI: https://eprints.soton.ac.uk/id/eprint/400065
PURE UUID: 77dde60d-f13d-450c-9e86-52c8084f176b
ORCID for Graham J. Tizzard: ORCID iD orcid.org/0000-0002-1577-5779
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 07 Sep 2016 10:37
Last modified: 15 Feb 2019 01:40

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Contributors

Author: Sarote Boonseng
Author: Gavin W. Roffe
Author: Rhiannon N. Jones
Author: Simon J. Coles ORCID iD
Author: John Spencer
Author: Hazel Cox

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