Experimental Evidence Supporting Related Mechanisms for Ru(II)-Catalyzed Dehydrocoupling and Hydrolysis of Amine-Boranes,ACS Catalysis

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Experimental Evidence Supporting Related Mechanisms for Ru(II)-Catalyzed Dehydrocoupling and Hydrolysis of Amine-Boranes
ACS Catalysis ( IF 11.3 ) Pub Date : 2017-11-09 00:00:00 , DOI: 10.1021/acscatal.7b02958
Ainara Telleria ₁ , Cristian Vicent ₂ , Virginia San Nacianceno ₁ , María A. Garralda ₁ , Zoraida Freixa _{1,

3}

Affiliation

A family of ruthenium(II) half-sandwich complexes was tested for the hydrolytic decomposition of amine-boranes. The analysis of the catalytic results, together with a multilateral approach based on ¹H, ¹¹B NMR, and ESI-MS were used to propose a plausible and conceptually unified mechanism for both the hydrolysis and competitive dehydrogenation of amine-boranes. We propose the intermediacy of solvent-stabilized borenium cations during the catalytic cycle, evolving toward dehydrogenation products in distilled THF or releasing amine-hydroxyboranes in aqueous media. Both reaction pathways would liberate up to 1 equivalent of hydrogen through a metal-catalyzed process, but an out-of-cycle low-barrier hydrolysis of amine-hydroxyboranes would produce the 2 additional equivalents of hydrogen in aqueous solutions. Metal-catalyzed deuteration of (non hydrogen-productive) trisubstituted amine-boranes by using D₂O as deuterium source was observed, and included as part of the mechanism proposal.

中文翻译：

Ru（II）催化胺-硼烷的脱氢偶联和水解的实验证据支持相关机理

测试了钌（II）半三明治配合物家族对胺-硼烷的水解分解作用。催化结果的分析，以及基于¹ H，¹¹的多边方法B NMR和ESI-MS用于为胺-硼烷的水解和竞争性脱氢提出一个合理且概念上统一的机理。我们提出了在催化循环中溶剂稳定的硼阳离子的中间产物，它在蒸馏的THF中趋向于脱氢产物或在水性介质中释放出胺-羟基硼烷。两种反应途径都可以通过金属催化的过程释放多达1当量的氢，但是胺-羟基硼烷的循环外低阻隔水解会在水溶液中产生另外2当量的氢。观察到以D ₂ O为氘源的金属催化的（非产氢的）三取代胺-硼烷的氘化反应，并将其作为机理建议的一部分。

更新日期：2017-11-09

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