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Pyranopterin Related Dithiolene Molybdenum Complexes as Homogeneous Catalysts for CO 2 Photoreduction
Author(s) -
Fogeron Thibault,
Retailleau Pascal,
Chamoreau LiseMarie,
Li Yun,
Fontecave Marc
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201809084
Subject(s) - formate , catalysis , chemistry , pyrazine , molybdenum , cobalt , formic acid , ligand (biochemistry) , ring (chemistry) , chelation , carbon monoxide , combinatorial chemistry , stereochemistry , inorganic chemistry , organic chemistry , biochemistry , receptor
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) 2 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 2 into formic acid, as the major product, and carbon monoxide, achieving more than 100 turnover numbers in about 8 h.