Structural and electronic studies of substituted m-terphenyl group 12 complexes

Valentine, Andrew J., Taylor, Laurence J., Geer, Ana M., Huke, Cameron D., Wood, Katherine E., Tovey, Will, Lewis, William, Argent, Stephen P., Teale, Andrew M., McMaster, Jonathan and Kays, Deborah L. ORCID: https://orcid.org/0000-0002-4616-6001 2022. Structural and electronic studies of substituted m-terphenyl group 12 complexes. Organometallics 41 (11) , pp. 1426-1433. 10.1021/acs.organomet.2c00156

Preview

PDF - Published Version Available under License Creative Commons Attribution. Download (1MB) | Preview

Abstract

The effects of para-substitution on the structural and electronic properties of four series of two-coordinate m-terphenyl Group 12 complexes (R-Ar#)2M (M = Zn, Cd, Hg; R = t-Bu 1–3, SiMe34–6, Cl 7–9, CF310–12, where R-Ar# = 2,6-{2,6-Xyl}2-4-R-C6H2 and 2,6-Xyl = 2,6-Me2C6H3) have been investigated. X-ray crystallography shows little structural variation across the series, with no significant change in the C–M–C bond distances and angles. However, considerable electronic differences are revealed by heteronuclear nuclear magnetic resonance (NMR) spectroscopy; a linear correlation is observed between the 113Cd, 199Hg, and 1H (2,6-Xyl methyl protons) NMR chemical shifts of the para-substituted complexes and the Hammett constants for the R-substituents. Specifically, an upfield shift in the NMR signal is observed with increasingly electron-withdrawing R-substituents. Density functional theory (DFT) calculations are employed to attempt to rationalize these trends.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	American Chemical Society
ISSN:	0276-7333
Date of First Compliant Deposit:	12 August 2024
Date of Acceptance:	30 May 2022
Last Modified:	12 Aug 2024 09:04
URI:	https://orca.cardiff.ac.uk/id/eprint/170344

Actions (repository staff only)

Edit Item