Journal
DALTON TRANSACTIONS
Volume 44, Issue 24, Pages 11165-11171Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5dt01366f
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Funding
- National Science Foundation of China [21372266, 21372268, 51302327, 21302148, 21390400, 21025206]
- 973 Program [2012CB725302]
- Foundation of 100YOUNG Chongqing University [0903005203191]
- Fundamental Research Funds for the Central Universities (Chongqing University) [106112015CDJZR228806]
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Employing the oxidative coupling of phenylacetylene with benzaldehyde as a model reaction, a density functional theory (DFT) study combined with extended X-ray absorption fine structure (EXAFS) experiment was carried out to reveal the difference between dinuclear and mononuclear zinc mediated nucleophilic addition. Newly reported DFT method M11-L computed results suggest that the mononuclear zinc mediated pathway, in which nucleophilic addition occurs via a four-membered ring transition state, is unfavourable both thermodynamically and kinetically. The dinuclear zinc mechanism, which appropriately explains the experimental observations, involves a six-membered ring transition state for nucleophilic addition. Subsequent in situ EXAFS experiment confirmed the existence of dinuclear zinc active species. Moreover, frontier molecular orbital (FMO) analysis and distortion-interaction energy analysis along the whole reaction pathways have provided interpretations for the advantage of dinuclear zinc mediated nucleophilic addition. Consequently, we believe this dinuclear zinc pathway will open up a general consideration of the dinuclear zinc mechanism for nucleophilic additions.
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