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Influence of hydrogen-bonding interactions on nuclearity and structure of palladium tiara-like complexes

Martin, Harry J.; Pfeiffer, Constance R.; Davies, E. Stephen; Davis, Adrienne L.; Lewis, William; Champness, Neil R.

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Authors

Harry J. Martin

Constance R. Pfeiffer

Adrienne L. Davis

William Lewis

Neil R. Champness



Abstract

The role of intramolecular hydrogen-bonding interactions upon the nuclearity of palladium tiara-like complexes is reported herein. The synthesis of three palladium tiaras is described with three related thiolate ligands that vary in their hydrogen-bonding capability, amide vs ester for Nacetylcysteamine (tiara 1) vs 2-mercaptoethyl acetate (tiara 2) or ethyl thioglycolate (tiara 3), and in the relative position of the ester group, 2-mercaptoethyl acetate (2) or ethyl thioglycolate (3). Mass spectrometry indicates that, in the absence of protic solvents, N-acetylcysteamine reacts to form exclusively a six-membered tiara, [Pd(SCH2CH2NHCOCH3)2]6, 1, whereas the ester containing analogues form both six- and eight-membered tiaras. Singlecrystal X-ray diffraction studies indicate the significance of intramolecular N−H···O hydrogen bonds in determining the nuclearity of the amide-containing tiara 1. NMR studies indicate that 1 is not in equilibrium with larger tiaras in solution, and that the smaller size of the aggregate inhibits the fluxional behavior of the pendant thiolate ligands, typically observed for larger tiaras. Electrochemical investigations of 1 reveal reductive processes that exhibit an increase in current upon addition of acid, along with the formation of palladium nanoparticles.

Journal Article Type Article
Acceptance Date Jul 25, 2018
Online Publication Date Aug 8, 2018
Publication Date Aug 31, 2018
Deposit Date Dec 21, 2018
Publicly Available Date Dec 21, 2018
Journal ACS Omega
Electronic ISSN 2470-1343
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 3
Issue 8
Pages 8769-8776
DOI https://doi.org/10.1021/acsomega.8b01133
Public URL https://nottingham-repository.worktribe.com/output/1436362
Publisher URL https://pubs.acs.org/doi/10.1021/acsomega.8b01133

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