On the Dewar-Chatt-Duncanson Model for Catalytic Gold(I) Complexes
On the Dewar-Chatt-Duncanson Model for Catalytic Gold(I) Complexes
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DOI：
10.1002/chem.201000608
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发表时间：
2010-01-01
影响因子：
4.3
通讯作者：
Tarantelli, Francesco
中科院分区：
文献类型：
--
作者：
Salvi, Nicola;Belpassi, Leonardo;Tarantelli, Francesco
本文对分子式为L-Au-I-S（L为N-杂环卡宾或Cl-，S为含C-C重键的η（2）配位底物）的催化中间体中的Dewar-Chatt-Duncanson模型中的电子电荷位移，给出了严格的无模型定义和详细的理论分析。因此，我们表明，与广泛持有的观点相反，金基板债券的特点是由一个大的π反馈捐赠组件，这是可比的，往往一样大，西格玛捐赠。的反馈捐赠被发现是一个高度可调的键组件，我们分析其与辅助配体L的性质和结构（相互依赖）的因素，如金属基板的键长和碳的pallialization的关系。
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.