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首页> 外文期刊>Organometallics >Mechanisms and Reactivity of TI(III) Main-Group-Metal Alkyl Functionalization in Water
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Mechanisms and Reactivity of TI(III) Main-Group-Metal Alkyl Functionalization in Water

机译：Ti（III）主要群 - 金属烷基官能化在水中的机制和反应性

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摘要

Metal-mediated C-H activation reactions generate metal alkyl intermediates that can be converted into carbon oxygen bonds through functionalization reactions. While the mechanisms and reactivity of C-H activation reactions have been well studied for transition-metal complexes, much less is known about functionalization reactions, especially for main-group-metal alkyl complexes. Here we report density functional theory calculations on the reaction thermodynamics and kinetic pathways for main-group, p-block-metal Tim methyl functionalization reactions in water using a combination of continuum and explicit/continuum solvent models. Specifically, we examined the oxygen functionalization of (OAc)T1(III)(CH3)(2) and (OAc)(2)T1(III)(CH3) in water where in both cases functionalization gives methyl acetate and methanol. Our calculations suggest that (OAc)T1(III)(CH3)(2) is thermodynamically and kinetically stable against bond homolysis, heterolysis, protonolysis, and all reductive functionalization pathways. Functionalization is only possible after methyl anion group transfer to TlIII(OAc)(3) to give (OAc)(2)T1(III)(CH3). Our calculations suggest that this monomethyl structure is functionalized by acetate dissociation to give a Tl monocation and then a one-step nucleophilic functionalization where water and acetate have competitive transition states.
机译：金属介导的C-H活化反应产生通过官能化反应转化为碳氧键的金属烷基中间体。虽然对过渡金属配合物进行了很好地研究了C-H活化反应的机制和反应性，但是对于官能化反应而言，尤其是用于主基金属烷基复合物的官能化反应而言。在这里，我们通过连续/连续/连续体溶剂模型的组合报告了在水中的反应热力学和动力学途径对水中的反应热力学和动力学途径进行了报告的密度函数理论计算，P-Block-Methm甲基官能化反应。具体地，我们检查了在水中的水中（OAC）T1（III）（2）（2）（2）T1（2）T1（III）（CH3）的氧官能化在两种情况下给予乙酸甲酯和甲醇。我们的计算表明（OAC）T1（III）（CH3）（2）在热力学上和动力学稳定，抵抗粘合均匀，异裂，质子溶解和所有还原官能化途径。官能化仅在甲基阴离子基团转移到TLIII（OAC）（3）之后可以给予（OAC）（2）T1（III）（CH3）。我们的计算表明，这种单甲基结构通过醋酸盐解离官能化，得到T1单位，然后是水和醋酸族具有竞争过渡状态的一步亲核官能化。

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