Correia José Tiago M, Nori Valeria, Jørgensen Mike S B, Nikol Alexander T, Nielsen Martin
Department of Chemistry, Technical University of Denmark, 2800 Kgs. Lyngby, Denmark.
Department of Fundamental Chemistry, Chemistry Institute, University of São Paulo, 05508-000 São Paulo, Brazil.
JACS Au. 2025 Apr 15;5(5):2114-2122. doi: 10.1021/jacsau.5c00051. eCollection 2025 May 26.
We demonstrate that bench-stable ruthenium-PNP nitrosyl complex salts with different counteranions (Cl, BF , BPh , PF , and OTs) and a ruthenium-POP nitrosyl complex are competent (pre)-catalysts for the CO hydrogenation to formic acid (FA) at low temperatures in ionic liquids. Only a minor effect of variation of the counteranion was observed, and weakly basic ionic liquids such as EMIM OAc, BMIM OAc, and EMIM HCO were suitable for this transformation, affording conversions up to 94 mol % formic acid compared to the ionic liquid (FA/IL) and turnover numbers (TONs) up to 1305. Importantly, the same catalytic system was also efficient for the dehydrogenation of formic acid back to CO and H, affording conversions up to >95% (949 TON) after 3 h at 95 °C. To investigate the application of such protocols for hydrogen storage and transportation purposes, hydrogenation/dehydrogenation cycles were performed, showing that this new catalytic system can promote up to 10 reversible CO hydrogenation/FA dehydrogenation cycles before losing its activity.
我们证明，具有不同抗衡阴离子（Cl、BF 、BPh 、PF 和OTs）的 bench-稳定的钌-PNP亚硝酰配合物盐以及钌-POP亚硝酰配合物是在离子液体中低温下将CO加氢生成甲酸（FA）的有效（预）催化剂。仅观察到抗衡阴离子变化的微小影响，并且弱碱性离子液体如EMIM OAc、BMIM OAc和EMIM HCO适用于这种转化，与离子液体相比，甲酸转化率高达94 mol%（FA/IL），周转数（TONs）高达1305。重要的是，相同的催化体系对甲酸脱氢回CO和H也很有效，在95℃下3小时后转化率高达>95%（949 TON）。为了研究此类方法在储氢和输氢方面的应用，进行了加氢/脱氢循环，结果表明这种新的催化体系在失去活性之前可以促进多达10次可逆的CO加氢/FA脱氢循环。
