Cadge, Jamie A, Bower, John F 
ORCID: 0000-0002-7551-8221 and Russell, Christopher A
(2021)
A Systematic Study of the Effects of Complex Structure on Aryl Iodide Oxidative Addition at Bipyridyl-Ligated Gold(I) Centers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 60 (47).
pp. 24976-24983.
Abstract
A combined theoretical and experimental approach has been used to study the unusual mechanism of oxidative addition of aryl iodides to [bipyAu(C<sub>2</sub> H<sub>4</sub> )]<sup>+</sup> complexes. The modular nature of this system allowed a systematic assessment of the effects of complex structure. Computational comparisons between cationic gold and the isolobal (neutral) Pd<sup>0</sup> and Pt<sup>0</sup> complexes revealed similar mechanistic features, but with oxidative addition being significantly favored for the group 10 metals. Further differences between Au and Pd were seen in experimental studies: studying reaction rates as a function of electronic and steric properties showed that ligands bearing more electron-poor functionality increase the rate of oxidative addition; in a complementary way, electron-rich aryl iodides give faster rates. This divergence in mechanism compared to Pd suggests that Ar-X oxidative addition with Au can underpin a broad range of new or complementary transformations.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | anion effects, bipyridyl, gold, ligand effects, oxidative addition |
| Divisions: | Faculty of Science and Engineering > School of Physical Sciences |
| Depositing User: | Symplectic Admin |
| Date Deposited: | 02 Nov 2021 14:15 |
| Last Modified: | 18 Jan 2023 21:25 |
| DOI: | 10.1002/anie.202108744 |
| Open Access URL: | https://doi.org/10.1002/anie.202108744 |
| Related URLs: | |
| URI: | https://livrepository.liverpool.ac.uk/id/eprint/3142517 |
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