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首页> 外文期刊>Organometallics >DFT study of an inner-sphere mechanism in the hydrogen transfer from a hydroxycyclopentadienyl ruthenium hydride to imines
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DFT study of an inner-sphere mechanism in the hydrogen transfer from a hydroxycyclopentadienyl ruthenium hydride to imines

机译：DFT研究氢从羟基环戊二烯基氢化钌转移到亚胺中的内球机理

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摘要

A combination of the DFT method with the computational description of environmental effects by solvent was applied to a theoretical study of the hydrogen transfer to imines by [2,3,4,5-Ph-4(eta(5)-C4COH)Ru(CO)(2)H] (2) within a molecular model that closely mimics the authentic reaction conditions. A consistent polarizable continuum solvent model (PCM) was instrumental and necessary in achieving stability of the computational model. Environmental effects by solvent were also considered in an extended model with an addition of explicit solvent molecules within the PCM. The study elucidates an inner-sphere mechanism in detail. Intermediate complexes and transition states are characterized. Three distinct energy barriers along the reaction coordinate are predicted when solvent effects are taken into account. The imine coordinates to ruthenium via ring slippage with an energy barrier of about 15 kcal/mol. Close in energy (12 kcal/mol) is the transition state of the hydride transfer, which gives an (eta(2)-cyclopentadienone)ruthenium amine intermediate. The presence of Ph groups on the Cp ring facilitates the ring slippage that occurs on imine coordination. This eta(2)-intermediate finally rearranges to the corresponding (eta(4)-cyclopentadienone)ruthenium amine complex via a transition state at 9 kcal/mol. The stable ruthenium amine complex was verified against an X-ray structure of the corresponding complex. Inclusion of the solvent (by PCM or explicit molecules) was required to stabilize low-hapticity intermediates and transition state structures.
机译：DFT方法与溶剂对环境影响的计算描述相结合，被用于通过[2,3,4,5-Ph-4（eta（5）-C4COH）Ru（ （CO）（2）H]（2）近似模拟真实的反应条件。一致的可极化连续介质溶剂模型（PCM）有助于实现计算模型的稳定性。在扩展模型中还考虑了溶剂对环境的影响，在PCM中添加了明确的溶剂分子。该研究详细阐明了内球机制。表征中间体配合物和过渡态。当考虑溶剂效应时，将预测沿着反应坐标的三个不同的能垒。亚胺通过环滑动以约15 kcal / mol的能垒与钌配位。氢化物转移的过渡态能量接近（12 kcal / mol），从而得到（eta（2）-环戊二烯酮）钌胺中间体。 Cp环上存在Ph基团有助于亚胺配位时发生的环滑移。该eta（2）-中间体最终以9 kcal / mol的过渡态重排为相应的（eta（4）-环戊二烯酮）钌胺络合物。针对相应配合物的X射线结构验证了稳定的钌胺配合物。需要包含溶剂（通过PCM或显式分子）来稳定低触觉性中间体和过渡态结构。

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