期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 16, 期 24, 页码 7231-7240出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201000608
关键词
coordination modes; density functional calculations; electronic structure; gold; homogeneous catalysis
资金
- Italian MIUR through FIRB
- PRIN
We provide a rigorous model-free definition and a detailed theoretical analysis of the electron-charge displacements making up the donation and back-donation components of the Dewar-Chatt-Duncanson model in some realistic catalytic intermediates of formula L-Au-I-S in which L is an N-heterocyclic carbene or Cl- and S is an eta(2)-coordinated Substrate containing a C-C multiple bond. We thus show, contrary to a widely held view, that the gold substrate bond is characterized by a large pi back-donation component that is comparable to, and often as large as, the sigma donation. The back-donation is found to be a highly tunable bond component and we analyze its relationship with the nature of the auxiliary ligand L and with structural (interdependent) factors such as metal substrate bond lengths and carbon pyramidalization.
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