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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >A computational study of cycloaddition reactions of d8 metal tetroxide (Iron, Ruthenium, Osmium) complexes with C_(60)
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A computational study of cycloaddition reactions of d8 metal tetroxide (Iron, Ruthenium, Osmium) complexes with C_(60)

机译：d8四氧化三铁（铁，钌，O）与C_（60）配合物环加成反应的计算研究

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摘要

The potential energy surfaces of the cycloaddition reactions MO _4(NC_5H_5)_2 + C_(60) → MO_4(NC_5H_5)_2(C_(60)) (M = Fe, Ru, and Os) have been studied at the B3LYP/LANL2DZ level of theory. It has been found that there should be two competing pathways in these reactions, which can be classified as a [6,5]-attack (path A) and a [6,6]-attack (path B). Our theoretical calculations indicate that, given the same reaction conditions, the cycloaddition reaction of C_(60)via [6,6]-attack is more favorable than that via [6,5]-attack both kinetically and thermodynamically. This is in good agreement with the available experimental observations. A qualitative model, which is based on the theory of Pross and Shaik, has been used to develop an explanation for the barrier heights. As a result, our theoretical findings suggest that the singlet-triplet splitting ΔE_(st) (= E _(triplet) - E_(singlet)) of the d~8 MO _4(NC_5H_5)_2 and C_(60) species can be a guide to predict their reactivity towards cycloaddition. Our model results demonstrate that the reactivity of d~8 metal tetroxide cycloaddition to C_(60) decreases in the order FeO_4(NC _5H_5)_2 > RuO_4(NC_5H _5)_2 > OsO_4(NC_5H_5) _2. In consequence, we show that both electronic and geometric effects play a decisive role in determining the energy barriers as well as the reaction enthalpy.
机译：在B3LYP / LANL2DZ能级上研究了环加成反应MO _4（NC_5H_5）_2 + C_（60）→MO_4（NC_5H_5）_2（C_（60））（M = Fe，Ru和Os）的势能面理论。已经发现在这些反应中应该有两个竞争途径，可以分为[6，5]攻击（路径A）和[6，6]攻击（路径B）。我们的理论计算表明，在相同的反应条件下，C_（60）通过[6,6]攻击的环加成反应比通过[6,5]攻击的动力学和热力学都更有利。这与现有的实验观察非常吻合。基于Pross和Shaik理论的定性模型已被用于解释障碍物高度。结果，我们的理论发现表明，d〜8 MO _4（NC_5H_5）_2和C_（60）物种的单重态-三重态分裂ΔE_（st）（= E _（triplet）-E_（singlet））可以是预测其对环加成反应的指南。我们的模型结果表明，d〜8金属四氧化物环加成物对C_（60）的反应性依次为FeO_4（NC _5H_5）_2> RuO_4（NC_5H _5）_2> OsO_4（NC_5H_5）_2。因此，我们表明，电子效应和几何效应在确定能垒以及反应焓方面都起着决定性的作用。

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