Metal-free hydrides are of increasing research interest due to their roles in recent scientific advances in catalysis, such as hydrogen activation with frustrated Lewis pairs and electrocatalytic CO₂ reduction with pyridinium and other aromatic cations. The structural design of hydrides for specific applications necessitates the correct description of their thermodynamic and kinetic prowess using reliable parameters – thermodynamic hydricity (ΔG_H⁻) and nucleophilicity (N). This review summarizes reported experimental and calculated hydricity values for more than 200 metal-free hydride donors, including carbon-, boron-, nitrogen- and silicon-based hydrides. We describe different experimental and computational methods used to obtain these thermodynamic and kinetic parameters. Furthermore, tabulated data on metal-free hydrides are discussed in terms of structure–property relationships, relevance to catalysis and contemporary limitations for replacing transition-metal hydride catalysts. Finally, several selected applications of metal-free hydrides in catalysis are described, including photosynthetic CO₂ reduction and hydrogen activation with frustrated Lewis pairs.

中文翻译：

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无金属氢化物的热力学和动力学水力学†

由于无金属氢化物在催化方面的最新科学进展中起着越来越重要的研究兴趣，例如在受挫的Lewis对中活化氢以及在吡啶鎓和其他芳香族阳离子中进行电催化还原CO ₂。氢化物的具体应用的结构设计必要使用可靠的参数其热力学和动力学实力的正确描述-热力学hydricity（Δ ģ _{ħ ^-} ）和亲核（Ñ）。这篇综述总结了200多种不含金属的氢化物供体（包括碳，硼，氮和硅基氢化物）的实验和计算的水合值。我们描述了用于获得这些热力学和动力学参数的不同实验和计算方法。此外，还根据结构与性质之间的关系，与催化作用的相关性以及替代过渡金属氢化物催化剂的现代局限性，对无金属氢化物的列表数据进行了讨论。最后，描述了几种不含金属的氢化物在催化中的选定应用，包括光合作用的CO ₂还原和沮丧的Lewis对对的氢活化。