Jump to main content
Jump to site search

Issue 24, 2015
Previous Article Next Article

Dinuclear versus mononuclear pathways in zinc mediated nucleophilic addition: a combined experimental and DFT study

Author affiliations

Abstract

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.

Graphical abstract: Dinuclear versus mononuclear pathways in zinc mediated nucleophilic addition: a combined experimental and DFT study

Back to tab navigation

Supplementary files

Publication details

The article was received on 10 Apr 2015, accepted on 08 May 2015 and first published on 08 May 2015


Article type: Paper
DOI: 10.1039/C5DT01366F
Author version available: Download Author version (PDF)
Citation: Dalton Trans., 2015,44, 11165-11171
  •   Request permissions

    Dinuclear versus mononuclear pathways in zinc mediated nucleophilic addition: a combined experimental and DFT study

    X. Qi, Y. Li, G. Zhang, Y. Li, A. Lei, C. Liu and Y. Lan, Dalton Trans., 2015, 44, 11165
    DOI: 10.1039/C5DT01366F

Search articles by author

Spotlight

Advertisements