Institut de Biologie Intégrative de la Cellule (I2BC), Institut des Sciences du Vivant Frédéric-Joliot, CEA Saclay, 91191, Gif-sur-Yvette, France.
Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes), UMR 6226, Rennes, F-35000, France.
Angew Chem Int Ed Engl. 2019 Mar 26;58(14):4504-4509. doi: 10.1002/anie.201814339. Epub 2019 Feb 20.
Inspired by nature's orchestra of chemical subtleties to activate and reduce CO , we have developed a family of iron porphyrin derivatives in to which we have introduced urea groups functioning as multipoint hydrogen-bonding pillars on the periphery of the porphyrinic ring. This structure closely resembles the hydrogen-bond stabilization scheme of the carbon dioxide (CO ) adduct in the carbon monoxide dehydrogenase (CODH). We found that such changes to the second coordination sphere significantly lowered the overpotential for CO reduction in this family of molecular catalysts and importantly increased the CO binding rate while maintaining high turnover frequency (TOF) and selectivity. Entrapped water molecules within the molecular clefts were found to be the source of protons for the CO reduction.
受大自然中微妙的化学交响乐启发，我们开发了一系列铁卟啉衍生物，其中引入了脲基团，作为卟啉环外围的多点氢键支柱。这种结构与一氧化碳脱氢酶（CODH）中二氧化碳（CO ）加合物的氢键稳定方案非常相似。我们发现，这种对第二配位层的改变显著降低了这个分子催化剂系列中 CO 还原的过电势，并且重要的是，在保持高周转频率（TOF）和选择性的同时，提高了 CO 结合速率。分子裂缝内捕获的水分子被发现是 CO 还原的质子来源。
