Synthesis and Reactivity of Mononuclear Iron Models of [Fe]‐Hydrogenase that Contain an Acylmethylpyridinol Ligand |
| |
| Authors: | Dr Bowen Hu Prof?Dr Dafa Chen Prof?Dr Xile Hu |
| |
| Institution: | 1. School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China);2. Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne (EPFL), ISIC‐LSCI, BCH 3305, 1015 Lausanne (Switzerland), Fax: (+41)?21‐693‐9305 |
| |
| Abstract: | Fe]‐hydrogenase has a single iron‐containing active site that features an acylmethylpyridinol ligand. This unique ligand environment had yet to be reproduced in synthetic models; however the synthesis and reactivity of a new class of small molecule mimics of Fe]‐hydrogenase in which a mono‐iron center is ligated by an acylmethylpyridinol ligand has now been achieved. Key to the preparation of these model compounds is the successful C?O cleavage of an alkyl ether moiety to form the desired pyridinol ligand. Reaction of solvated complex (2‐CH2CO‐6‐HOC5H3N)Fe(CO)2(CH3CN)2]+(BF4)? with thiols or thiophenols in the presence of NEt3 yielded 5‐coordinate iron thiolate complexes. Further derivation produced complexes (2‐CH2CO‐6‐HOC5H3N)Fe(CO)2(SCH2CH2OH)] and (2‐CH2CO‐6‐HOC5H3N)Fe(CO)2(CH3COO)], which can be regarded as models of FeGP cofactors of Fe]‐hydrogenase extracted by 2‐mercaptoethanol and acetic acid, respectively. When the derivative complexes were treated with HBF4?Et2O, the solvated complex was regenerated by protonation of the thiolate ligands. The reactivity of several models with CO, isocyanide, cyanide, and H2 was also investigated. |
| |
| Keywords: | carbonyl complexes enzyme models hydrogenases iron thiolates |
|
|
