Proton to hydride umpolung at a phosphonium center via electron relay: a new strategy for main-group based water reduction,Chemical Science

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Proton to hydride umpolung at a phosphonium center via electron relay: a new strategy for main-group based water reduction
Chemical Science ( IF 7.6 ) Pub Date : 2021-11-15 , DOI: 10.1039/d1sc05135k
Takumi Oishi ₁ , Leonardo I Lugo-Fuentes ₂ , Yichuan Jing ₁ , J Oscar C Jimenez-Halla ₂ , Joaquín Barroso-Flores _{3,

4} , Masaaki Nakamoto ₁ , Yohsuke Yamamoto ₁ , Nao Tsunoji ₅ , Rong Shang ₁

Affiliation

Generation of dihydrogen from water splitting, also known as water reduction, is a key process to access a sustainable hydrogen economy for energy production and usage. The key step is the selective reduction of a protic hydrogen to an accessible and reactive hydride, which has proven difficult at a p-block element. Although frustrated Lewis pair (FLP) chemistry is well known for water activation by heterolytic H–OH bond cleavage, to the best of our knowledge, there has been only one case showing water reduction by metal-free FLP systems to date, in which silylene (Si^II) was used as the Lewis base. This work reports the molecular design and synthesis of an ortho-phenylene linked bisborane-functionalized phosphine, which reacts with water stoichiometrically to generate H₂ and phosphine oxide quantitatively under ambient conditions. Computational investigations revealed an unprecedented multi-centered electron relay mechanism offered by the molecular framework, shuttling a pair of electrons from hydroxide (OH⁻) in water to the separated proton through a borane-phosphonium-borane path. This simple molecular design and its water reduction mechanism opens new avenues for this main-group chemistry in their growing roles in chemical transformations.

中文翻译：

通过电子中继在鏻中心将质子转化为氢化物：一种基于主族的减水新策略

通过水分解产生氢气（也称为水还原）是实现能源生产和使用可持续氢经济的关键过程。关键步骤是将质子氢选择性还原为可接近且具有反应性的氢化物，这在 p 区元素中已被证明是困难的。尽管受阻路易斯对 (FLP) 化学因异解 H-OH 键断裂而使水活化而闻名，但据我们所知，迄今为止只有一种情况表明无金属 FLP 系统可减少水，其中亚硅基(Si ^II )用作路易斯碱。这项工作报道了邻亚苯基连接的双硼烷官能化膦的分子设计和合成，该膦在环境条件下与水化学计量反应，定量生成H ₂和氧化膦。计算研究揭示了分子框架提供的前所未有的多中心电子中继机制，通过硼烷-鏻-硼烷路径将一对电子从水中的氢氧化物（OH ^- ）穿梭到分离的质子。这种简单的分子设计及其减水机制为这种主族化学在化学转化中发挥日益重要的作用开辟了新的途径。

更新日期：2021-11-25

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