活性有机金化合物特性与相关催化反应的理论研究

By means of more quantum chemical methods, we will conduct a systematic theoretical investigation regarding, i) the electronic structures,chemical bonding and reactivity of various of active organogold species that are widely involved as precursors and intermediates in homogeneous gold-catalyzed organic transformations, ii) the effects of substituents on substrates,ancillary ligands,and solvents on the chemical bonding and reactivity of these active organogold complexes,iii) the reactions of various small molecules (as probes) with these organspecies, trying to establish a thorough understanding and a solid theretical basis of the chemistry of these active organogold species.Also we will employ quantum chemical methods and, if necessary, molecular dynamics methods to investigation the reaction pathways, energetics and kinetics of various representative gold-catalyzed organic reactions as well as the effects of ancillary ligands,solvents,substrates,additives，counterions and temerature on the reaction mechanisms, energetics,kinetics,and (chemo-, regio-, stereo-)selectivities of these selected reactions.Also we shall try to design some new gold-catalyzed organic reactions of high efficiency,controllability and selectivity with the help of quantum chemical calculations.We hope, upon completion of this project,that a systematic theory of homogeneous gold catalysis can be estabilished, which will be of significance for the design and development of highly controllable and highly selective gold-catalyzed organic transformations that are of industrial importance.

运用现代量子化学手段，系统地探讨金均相催化反应体系中可能出现的各类活性有机金化合物(包括前驱体和中间体)的电子结构、成键及反应性以及底物取代基、辅助配体、溶剂等效应对其成键和反应性的影响机制，利用探针分子（各种无机有机小分子）探讨它们的反应规律，以期构筑较为系统的有机金化合物化学的理论体系；运用现代量子化学手段结合动力学手段，探讨一系列代表性的金催化反应的反应机理，探讨不同反应环境（包括辅助配体、溶剂、底物、助剂、抗衡离子、温度等）对反应机理、能学和（化学、区域及立体）选择性的影响和调控机制，以期能在一定程度上构筑金均相催化的理论体系；进而预测一些具有实用价值、导向明确的金催化有机反应。我们也期望，本项目的研究，能够为理论预测、设计和发展高效可控、导向明确且具有工业价值的金催化有机反应提供理论基础。

运用现代量子化学手段，系统地探讨了金均相催化反应体系中可能出现的各类活性有机金化合物(包括前驱体和中间体)的电子结构、成键及反应性以及底物取代基、辅助配体、溶剂等效应对其成键和反应性的影响机制，利用探针分子（各种无机有机小分子）探讨它们的反应规律；运用现代量子化学手段结合动力学手段，探讨一系列代表性的金催化反应的反应机理，探讨不同反应环境（包括辅助配体、溶剂、底物、助剂、抗衡离子、温度等）对反应机理、能学和（化学、区域及立体）选择性的影响和调控机制；与实验合作者共同发展了一些具有实用价值、导向明确的金催化有机反应。本项目的研究，为理论预测、设计和发展高效可控、导向明确且具有工业价值的金催化有机反应提供理论基础。