Enabling Semihydrogenation of Alkynes to Alkenes by Using a Calcium Palladium Complex Hydride,Journal of the American Chemical Society

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Enabling Semihydrogenation of Alkynes to Alkenes by Using a Calcium Palladium Complex Hydride
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-12-02 , DOI: 10.1021/jacs.1c09489
Qing Guo _{1,

2} , Ruting Chen ₃ , Jianping Guo _{1,

2} , Chao Qin ₁ , Zhitao Xiong ₁ , Hanxue Yan _{1,

2} , Wenbo Gao _{1,

2} , Qijun Pei ₁ , Anan Wu ₃ , Ping Chen _{1,

2}

Affiliation

Selective hydrogenation of alkynes to alkenes requires a catalytic site with suitable electronic properties for modulating the adsorption and conversion of alkyne, alkene as well as dihydrogen. Here, we report a complex palladium hydride, CaPdH₂, featured by electron-rich [PdH₂]^δ− sites that are surrounded by Ca cations that interacts with C₂H₂ and C₂H₄ via σ-bonding to Pd and unusual cation−π interaction with Ca, resulting in a much weaker chemisorption than those of Pd metal catalysts. Concomitantly, the dissociation of H₂ and hydrogenation of C₂H_x (x = 2–4) species experience significant energy barriers over CaPdH₂, which is fundamentally different from those reported Pd-based catalysts. Such a unique catalytic environment enables CaPdH₂, the very first complex transition-metal hydride catalyst, to afford a high alkene selectivity for the semihydrogenation of alkynes.

中文翻译：

使用钙钯络合物氢化物使炔烃半氢化成烯烃

炔烃选择性氢化成烯烃需要具有合适电子特性的催化位点，以调节炔烃、烯烃以及二氢的吸附和转化。在这里，我们报告了一种复杂的氢化钯 CaPdH ₂，其特征是富电子 [PdH ₂ ] ^δ−位点被 Ca 阳离子包围，Ca 阳离子通过 σ 键与 Pd 和不寻常的C ₂ H ₂和 C ₂ H ₄相互作用阳离子-π 与 Ca 的相互作用，导致比 Pd 金属催化剂更弱的化学吸附。同时，H ₂的解离和C ₂ H _x ( x= 2–4) 物种在 CaPdH _{2 上}经历了显着的能量障碍，这与报道的那些基于 Pd 的催化剂有着根本的不同。这种独特的催化环境使 CaPdH ₂成为第一种复杂的过渡金属氢化物催化剂，能够为炔烃的半氢化提供高烯烃选择性。

更新日期：2021-12-15

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