Fogeron Thibault, Retailleau Pascal, Chamoreau Lise-Marie, Li Yun, Fontecave Marc
Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Collège de France, Université Paris Sorbonne, 11 Place Marcelin Berthelot, 75231, Paris Cedex 05, France.
Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Université Paris-Saclay, 1, av.de la Terrasse, 91198, Gif-sur-Yvette, France.
Angew Chem Int Ed Engl. 2018 Dec 21;57(52):17033-17037. doi: 10.1002/anie.201809084. Epub 2018 Nov 28.
Two original dithiolenes, with a pyrazine ring fused with a pyran ring carrying the dithiolene chelate, mimicking molybdopterin (MPT) present in the active site of formate dehydrogenases (FDHs), have been synthesized. The first one mimicks MPT in the dihydropyrazine form while the second mimicks MPT in the more biologically relevant tetrahydropyrazine form. Both have been structurally characterized as a ligand within a cobalt(cyclopentadienyl)(dithiolene) complex. The corresponding MoO(dithiolene) complexes have been also prepared and are reported as the first functional and stable catalysts inspired by the Mo center of FDHs so far: they indeed catalyze the photoreduction of CO into formic acid, as the major product, and carbon monoxide, achieving more than 100 turnover numbers in about 8 h.
已合成了两种原始的二硫纶，它们具有与携带二硫纶螯合物的吡喃环稠合的吡嗪环，模拟了甲酸脱氢酶（FDHs）活性位点中存在的钼蝶呤（MPT）。第一种模拟二氢吡嗪形式的MPT，而第二种模拟生物学上更相关的四氢吡嗪形式的MPT。两者均已在钴（环戊二烯基）（二硫纶）配合物中作为配体进行了结构表征。还制备了相应的MoO（二硫纶）配合物，据报道这是迄今为止受FDHs的Mo中心启发而得到的首批功能性稳定催化剂：它们确实催化CO光还原为主要产物甲酸和一氧化碳，在约8小时内实现了超过100的周转数。
