Unravelling the mechanism of tin-based frustrated Lewis pair catalysed hydrogenation of carbonyl compounds†,Catalysis Science & Technology

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Unravelling the mechanism of tin-based frustrated Lewis pair catalysed hydrogenation of carbonyl compounds†
Catalysis Science & Technology ( IF 4.4 ) Pub Date : 2018-08-30 00:00:00 , DOI: 10.1039/c8cy01227j
Shubhajit Das _{1,

2,

3,

4} , Swapan K. Pati _{1,

2,

3,

4,

5}

Affiliation

This article presents a comprehensive study on the mechanism of Sn/N frustrated Lewis pair (FLP) catalysed hydrogenation of carbonyl compounds to corresponding alcohols. Possible reaction pathways have been elucidated in detail using density functional theory computations. The reaction begins with Sn/N FLP-mediated heterolytic cleavage of a H₂ molecule to release active hydrogens in solution. Our results reveal that, instead of the usual Brønsted acid activation, the carbonyl substrate is activated by Lewis acid complexation, followed by subsequent hydride and proton delivery to complete the hydrogenation process. Additionally, we have also examined the feasibility of an autocatalytic pathway. The main feature of this reaction route is Sn/O FLP-mediated H₂ cleavage, which has a comparable barrier to H₂ splitting by Sn/N FLPs. Overall, our computational mechanistic model is consistent with the experimental findings and the computed free energy barriers are in good agreement with the observed reactivity at experimental temperature. Insights obtained from this study are crucial for the rational development of Sn-based FLP hydrogenation catalysts.

中文翻译：

阐明锡基沮丧的路易斯对催化羰基化合物氢化的机理†

本文对Sn / N抑制的路易斯对（FLP）催化羰基化合物加氢生成相应醇的机理进行了全面的研究。使用密度泛函理论计算已详细阐明了可能的反应途径。反应开始于Sn / N FLP介导的H ₂分子的异源裂解，以释放溶液中的活性氢。我们的结果表明，与通常的布朗斯台德酸活化不同，羰基底物通过路易斯酸络合被活化，随后通过氢化物和质子输送完成氢化过程。此外，我们还研究了自催化途径的可行性。该反应路线的主要特征是Sn / O FLP介导的H ₂裂解，这对Sn / N FLP分解H ₂具有可比的障碍。总的来说，我们的计算机理模型与实验结果是一致的，并且计算出的自由能垒与在实验温度下观察到的反应性非常吻合。从这项研究中获得的见解对于合理开发锡基FLP加氢催化剂至关重要。

更新日期：2018-08-30

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