Chaudhary Karan, Trivedi Manoj, Masram D T, Kumar Abhinav, Kumar Girijesh, Husain Ahmad, Rath Nigam P
Department of Chemistry, University of Delhi, Delhi-110007, India.
Department of Chemistry, University of Lucknow, Lucknow-226007, India.
Dalton Trans. 2020 Mar 3;49(9):2994-3000. doi: 10.1039/c9dt04662c.
Carbon dioxide (CO2) is an important reactant and can be used for the syntheses of various types of industrially important chemicals. Hence, investigation concerning the conversion of CO2 into valuable energy-rich chemicals is an important and current topic in molecular catalysis. Recent research on molecular catalysts has led to improved rates for conversion of CO2 to energy-rich products such as formate, but the catalysts based on first-row transition metals are underdeveloped. Copper(i) complexes containing the 1,1'-bis(di-tert-butylphosphino) ferrocene ligand were found to promote the catalytic hydrogenation of CO2 to formate in the presence of DBU as the base, where the catalytic conversion of CO2via hydrogenation is achieved using in situ gaseous H2 (granulated tin metal and concentrated HCl) to produce valuable energy-rich chemicals, and therefore it is a promising, safe and simple strategy to conduct reactions under ambient pressure at room temperature. Towards this goal, we report an efficient copper(i) complex based catalyst [CuI(dtbpf)] to achieve ambient-pressure CO2 hydrogenation catalysis for generating the formate salt (HCO2-) with turnover number (TON) values of 326 to 1.065 × 105 in 12 to 48 h of reaction at 25 °C to 80 °C. The outstanding catalytic performance of [CuI(dtbpf)] makes it a potential candidate for realizing the large-scale production of formate by CO2 hydrogenation.
二氧化碳（CO₂）是一种重要的反应物，可用于合成各类具有重要工业价值的化学品。因此，研究将CO₂转化为有价值的富含能量的化学品是分子催化领域一个重要的前沿课题。近期对分子催化剂的研究提高了CO₂转化为甲酸等富含能量产物的速率，但基于第一周期过渡金属的催化剂仍未得到充分发展。人们发现，含有1,1'-双（二叔丁基膦基）二茂铁配体的铜（Ⅰ）配合物，在作为碱的1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）存在下，能促进CO₂催化加氢生成甲酸，其中通过原位气态H₂（粒状锡金属和浓盐酸）实现CO₂加氢催化转化，从而生成有价值的富含能量的化学品，因此在室温常压下进行反应是一种有前景、安全且简便的策略。为实现这一目标，我们报道了一种高效的基于铜（Ⅰ）配合物的催化剂[CuI(dtbpf)]，该催化剂在25℃至80℃下反应12至48小时，能实现常压CO₂加氢催化生成甲酸盐（HCO₂⁻），周转数（TON）值为326至1.065×10⁵。[CuI(dtbpf)]出色的催化性能使其成为通过CO₂加氢实现大规模生产甲酸盐的潜在候选物。
