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Inorganics 2016, 4(3), 25; doi:10.3390/inorganics4030025

The Trans Influence in Unsymmetrical Pincer Palladacycles: An Experimental and Computational Study

1
Department of Chemistry, School of Life Sciences, University of Sussex, Falmer, Brighton, East Sussex, BN1 9QJ, UK
2
UK National Crystallography Service, School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, UK
*
Authors to whom correspondence should be addressed.
Academic Editor: Duncan H. Gregory
Received: 24 June 2016 / Revised: 3 August 2016 / Accepted: 5 August 2016 / Published: 11 August 2016
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
View Full-Text   |   Download PDF [2964 KB, uploaded 11 August 2016]   |  

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. View Full-Text
Keywords: pincer palladacycles; density functional theory; atoms in molecules; trans influence pincer palladacycles; density functional theory; atoms in molecules; trans influence
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MDPI and ACS Style

Boonseng, S.; Roffe, G.W.; Jones, R.N.; Tizzard, G.J.; Coles, S.J.; Spencer, J.; Cox, H. The Trans Influence in Unsymmetrical Pincer Palladacycles: An Experimental and Computational Study. Inorganics 2016, 4, 25.

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