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中文摘要：
用密度泛函理论（DFT）方法对一系列A3型咔咯锰（V）氧配合物进行了理论计算．结果表明：咔咯锰（V）-氧配合物中Mn—O键是由1个σ键和2个π键构成的叁键结构：当咔咯中位取代基由推电子过渡到拉电子性质时，咔咯骨架紧缩，Mn-O键缩短，其拉曼光谱的伸缩振动峰往高波数移动：取代基与氧原子的静电作用模式由正-负吸引转化为负一负排斥，导致Mn-O键解离能△E减少，即拉电子基团有利于增强咔咯锰（V）-氧配合物氧原子的活泼性．
英文摘要：
Density functional theory （DFT） calculations are used to investigate the effect of substituents on the Mn - O bond in A3-type oxo-manganese（V） corrole complexes. Results indicate that the Mn - O bonds in all the investigated oxo-manganese（V） corrole complexes are triply bonded by one a and two π bonds. As the electron withdrawing ability of the substituents increases, the corrole skeleton contracts, resulting in a decrease in the Mn- O bond length, and the Mn- O Raman stretching vibration shifts to higher wavenumber. As the electrostatic potential of the substituents changes from positive to negative, the electrostatic interaction between oxygen and substituents changes from a negative-positive electrostatic attraction to a negative-negative electrostatic repulsion. Electron withdrawing substituents enhance oxygen reactivity of corrole Mn-oxo complexes by lowering the Mn-O bond dissociation energy.
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