Structural and electronic studies of substituted m-terphenyl group 12 complexes
| Autor: | Andrew J. Valentine, Laurence J. Taylor, Ana M. Geer, Cameron D. Huke, Katherine E. Wood, Will Tovey, William Lewis, Stephen P. Argent, Andrew M. Teale, Jonathan McMaster, Deborah L. Kays |
|---|---|
| Přispěvatelé: | Engineering and Physical Sciences Research Council (UK), European Commission, University of Nottingham |
| Jazyk: | angličtina |
| Rok vydání: | 2022 |
| Předmět: | |
| Zdroj: | Zaguán. Repositorio Digital de la Universidad de Zaragoza instname |
| ISSN: | 0276-7333 1520-6041 |
| Popis: | 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. The authors acknowledge the EPSRC [Grant Numbers EP/R004064/1 and EP/L015633/1]; the Leverhulme Trust [Grant Number RPG-2014-317]; the European Research Council under H2020/ERC Consolidator Grant “topDFT” [Grant Number 772259]; and the University of Nottingham for financial support of this research. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|