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

Valentine, A. J. ; Taylor, L. J. ; Geer, A. M. ; Huke, C. D. ; Wood, K. E. ; Tovey, W. ; Lewis, W. ; Argent, S. P. ; Teale, A. M. ; McMaster, J. ; Kays, D. L.

Resumen: 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, SiMe3 4-6, Cl 7-9, CF3 10-12, 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. © 2022 The Authors. Published by American Chemical Society.

Idioma: Inglés

DOI: 10.1021/acs.organomet.2c00156

Año: 2022

Publicado en: Organometallics 41, 11 (2022), 1426–1433
ISSN: 0276-7333

Factor impacto JCR: 2.8 (2022)

Categ. JCR: CHEMISTRY, ORGANIC rank: 16 / 52 = 0.308 (2022) - Q2 - T1
Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 16 / 42 = 0.381 (2022) - Q2 - T2

Factor impacto CITESCORE: 6.6 - Chemistry (Q1)

Factor impacto SCIMAGO: 0.868 - Inorganic Chemistry (Q1) - Physical and Theoretical Chemistry (Q1) - Organic Chemistry (Q1)

Tipo y forma: Artículo (Versión definitiva)