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Experimental and four‐component relativistic DFT studies of tungsten carbonyl complexes
Author(s) -
Demissie Taye B.,
Kostenko Nataliya,
Komorovsky Stanislav,
Repisky Michal,
Isaksson Johan,
Bayer Annette,
Ruud Kenneth
Publication year - 2015
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3476
Subject(s) - chemistry , relativistic quantum chemistry , chemical shift , density functional theory , tungsten , computational chemistry , molecule , atomic physics , organic chemistry , physics
Abstract We present a theoretical and experimental study of the structure and nuclear magnetic resonance (NMR) parameters of the pentacarbonyltungsten complexes of η 1 ‐2‐(trimethylstannyl)‐4,5‐dimethylphosphinine, η 2 ‐norbornene, and imidazolidine‐2‐thione. The three complexes have a pseudo ‐octahedral molecular structure with the six ligands bonded to the tungsten atom. The η 1 ‐2‐(trimethylstannyl)‐4,5‐dimethylphosphinine‐pentacarbonyl tungsten complex was synthesized for the first time. For all compounds, we present four‐component relativistic calculations of the NMR parameters at the Dirac–Kohn–Sham density functional level of theory using hybrid functionals. These large‐scale relativistic calculations of NMR chemical shifts and spin–spin coupling constants were compared with available experimental data, either taken from the literature or measured in this work. The inclusion of solvent effects modeled using a conductor‐like screening model was found to improve agreement between the calculated and experimental NMR parameters, and our best estimates for the NMR parameters are generally in good agreement with available experimental results. The present work demonstrates that four‐component relativistic theory has reached a level of maturity that makes it a convenient and accurate tool for modeling and understanding chemical shifts and indirect spin–spin coupling constants of organometallic compounds containing heavy elements, for which conventional non‐relativistic theory breaks down. Copyright © 2015 John Wiley & Sons, Ltd.