Hydrogenation of CO2 to Formic Acid with a Highly Active Ruthenium Acriphos Complex in DMSO and DMSO/Water.
Hydrogenation of CO2 to Formic Acid with a Highly Active Ruthenium Acriphos Complex in DMSO and DMSO/Water.
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DOI：
10.1002/anie.201603878
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发表时间：
2016-07-25
影响因子：
16.6
通讯作者：
Leitner, Walter
中科院分区：
文献类型：
--
作者：
Rohmann, Kai;Kothe, Jens;Haenel, Matthias W.;Englert, Ulli;Hoelscher, Markus;Leitner, Walter
新型的[Ru(Acriphos)(PPh3)(Cl)(PhCO2)][1；Acriphos=4，5-双(二苯基膦)吖啶]是一种性能优良的预催化剂，用于二氧化碳在二甲基亚砜(DMSO)和DMSO/H2O中加氢生成甲酸，而不需要胺碱作为共试剂。获得了高达4200个循环次数(吨)和高达260 h−1的循环频率(TOF)，从而使1成为迄今报道的在无添加剂条件下二氧化碳加氢反应最活跃的催化剂之一。通过密度泛函理论计算，合理地解释了反应介质通过甲酸与溶剂或水的簇合物之间的氢键对反应产物的热力学稳定作用。实验结果表明，在催化条件下得到的甲酸最终浓度较低(0.33 L−1)，这是由产物依赖的催化剂抑制所限制的，而不是热力学限制，可以通过添加少量的醋酸盐缓冲液来克服，从而使游离甲酸的最大浓度达到1.27 moL L−1，这与最佳值TON=16×10 3和TOFavg≈10 3 h−1相对应。
The novel [Ru(Acriphos)(PPh3)(Cl)(PhCO2)] [1; Acriphos=4,5‐bis(diphenylphosphino)acridine] is an excellent precatalyst for the hydrogenation of CO2 to give formic acid in dimethyl sulfoxide (DMSO) and DMSO/H2O without the need for amine bases as co‐reagents. Turnover numbers (TONs) of up to 4200 and turnover frequencies (TOFs) of up to 260 h−1 were achieved, thus rendering 1 one of the most active catalysts for CO2 hydrogenations under additive‐free conditions reported to date. The thermodynamic stabilization of the reaction product by the reaction medium, through hydrogen bonds between formic acid and clusters of solvent or water, were rationalized by DFT calculations. The relatively low final concentration of formic acid obtained experimentally under catalytic conditions (0.33 mol L−1) was shown to be limited by product‐dependent catalyst inhibition rather than thermodynamic limits, and could be overcome by addition of small amounts of acetate buffer, thus leading to a maximum concentration of free formic acid of 1.27 mol L−1, which corresponds to optimized values of TON=16×103 and TOFavg≈103 h−1.
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影响因子：
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