Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 47, Pages 24976-24983Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202108744
Keywords
anion effects; bipyridyl; gold; ligand effects; oxidative addition
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Funding
- EPSRC [EP/L015366/1]
- University of Bristol
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A combined theoretical and experimental investigation revealed an unusual mechanism of aryl iodide oxidative addition to gold complexes. The comparison between gold and palladium demonstrated significant differences in reaction rates and mechanisms, suggesting that gold could potentially facilitate a broad range of new or complementary transformations.
A combined theoretical and experimental approach has been used to study the unusual mechanism of oxidative addition of aryl iodides to [bipyAu(C2H4)](+) 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-0 and Pt-0 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.
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