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Mechanistic analysis of the photochemical carboxylation of o-alkylphenyl ketones with carbon dioxide

机译：二氧化碳O-烷基苯基酮的光化学羧化机械分析

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The mechanisms for photochemical carboxylation reactions are studied theoretically using two model systems: o -methylbenzophenone and o -methylacetophenone, with the M06-L and the 6-311G(d,p) basis set. Three reaction routes are used to ascertain the actual photochemical reaction mechanism for the o -alkylphenyl ketone molecules. The structures of the intersystem crossing, which play a central role in these photocarboxylations, are determined. The intermediates and transition structures for the ground singlet states and the excited triplet states are also computed to allow a qualitative interpretation of the entire reaction path. The theoretical findings show that when o -alkylphenyl ketone molecules are produced in the T _(1) state by photoexcitation at 365 nm, intersystem crossing to the S _(0) surface is the most probable pathway for deactivation. When they relax to the S _(0) state, the o -alkylphenyl ketone molecules can either react with CO _(2) to undergo the insertion reaction, which produces the carboxylic acid, or revert to the reactants. In particular, the theoretical investigations strongly suggest that the insertion of CO _(2) in these photocarboxylation reactions for o -alkylphenyl ketones occurs on the S _(0) surface, rather than on the excited T _(1) surface.
机译：从理论上使用两种模型系统研究光化学羧化反应的机制：O-甲基二苯甲酮和O-甲基乙酮，用M06-L和6-311g（D，P）的基础设定。三种反应途径用于确定O-烷基苯基酮分子的实际光化学反应机制。确定在这些光羧基中起核心作用的基于系统交叉的结构。还计算了地面态态的中间体和过渡结构和激发三重态状态以允许对整个反应路径进行定性解释。理论发现表明，当通过365nm的光透镜在T _（1）状态下在T _（1）状态中产生O-烷基苯基酮分子时，交叉于S _（0）表面的间隙是最可能的停用途径。当它们放松到S _（0）状态时，O-烷基苯基酮分子可以与CO _（2）反应以经历插入反应，其产生羧酸，或者恢复到反应物中。特别地，理论研究强烈表明，在S _（0）表面上发生O-烷基苯基酮的这些光羧化反应中的CO _（2）的插入，而不是在激发的T _（1）表面上。

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