A Bimetallic Nickel–Gallium Complex Catalyzes CO2 Hydrogenation via the Intermediacy of an Anionic d10 Nickel Hydride,Journal of the American Chemical Society

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A Bimetallic Nickel–Gallium Complex Catalyzes CO2 Hydrogenation via the Intermediacy of an Anionic d10 Nickel Hydride
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-09-28 00:00:00 , DOI: 10.1021/jacs.7b07911
Ryan C. Cammarota ₁ , Matthew V. Vollmer ₁ , Jing Xie _{1,

2} , Jingyun Ye _{1,

2} , John C. Linehan ₃ , Samantha A. Burgess ₃ , Aaron M. Appel ₃ , Laura Gagliardi _{1,

2} , Connie C. Lu ₁

Affiliation

Large-scale CO₂ hydrogenation could offer a renewable stream of industrially important C₁ chemicals while reducing CO₂ emissions. Critical to this opportunity is the requirement for inexpensive catalysts based on earth-abundant metals instead of precious metals. We report a nickel–gallium complex featuring a Ni(0)→Ga(III) bond that shows remarkable catalytic activity for hydrogenating CO₂ to formate at ambient temperature (3150 turnovers, turnover frequency = 9700 h^–1), compared with prior homogeneous Ni-centered catalysts. The Lewis acidic Ga(III) ion plays a pivotal role in stabilizing catalytic intermediates, including a rare anionic d¹⁰ Ni hydride. Structural and in situ characterization of this reactive intermediate support a terminal Ni–H moiety, for which the thermodynamic hydride donor strength rivals those of precious metal hydrides. Collectively, our experimental and computational results demonstrate that modulating a transition metal center via a direct interaction with a Lewis acidic support can be a powerful strategy for promoting new reactivity paradigms in base-metal catalysis.

中文翻译：

双金属镍-镓络合物通过阴离子d ¹⁰氢化镍的中间体催化CO ₂加氢。

大规模CO ₂加氢可以提供可再生的工业上重要的C ₁化学品流，同时减少CO ₂排放量。对于这种机会至关重要的是，需要廉价的催化剂，这些催化剂应以富含地球的金属而不是贵金属为基础。我们报道了一种具有Ni（0）→Ga（III）键的镍-镓络合物，与以前的均相相比，该络合物在环境温度下具有显着的催化CO ₂加氢成甲酸酯的催化活性（3150周转，周转频率= 9700 h ^–1）。镍中心催化剂。路易斯酸性Ga（III）离子在稳定催化中间体（包括稀有阴离子d ¹⁰ Ni氢化物）中起关键作用。结构和该反应性中间体的原位表征支持一个Ni-H末端部分，为此，热力学氢化物供体的强度可与贵金属氢化物相媲美。总的来说，我们的实验和计算结果表明，通过与路易斯酸性载体的直接相互作用调节过渡金属中心可能是促进贱金属催化新反应性范例的强大策略。

更新日期：2017-09-28

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