3 years ago

Pyranopterin Related Dithiolene Molybdenum Complexes as Homogeneous Catalysts for CO2 Photoreduction

Thibault Fogeron, Pascal Retailleau, Lise-Marie Chamoreau, Yun Li, Marc Fontecave

Abstract

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 Co(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 CO2 into formic acid, as the major product, and carbon monoxide, achieving more than 100 turnover numbers in about 8 h.

Publisher URL: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201809084

DOI: 10.1002/anie.201809084

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