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Synthesis and Reactivity of Mononuclear Iron Models of [Fe]‐Hydrogenase that Contain an Acylmethylpyridinol Ligand
Author(s) -
Hu Bowen,
Chen Dafa,
Hu Xile
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201304290
Subject(s) - hydrogenase , chemistry , reactivity (psychology) , ligand (biochemistry) , moiety , medicinal chemistry , stereochemistry , isocyanide , protonation , pivalic acid , heterolysis , enzyme , organic chemistry , catalysis , medicine , ion , biochemistry , alternative medicine , receptor , pathology
[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 CO cleavage of an alkyl ether moiety to form the desired pyridinol ligand. Reaction of solvated complex [(2‐CH 2 CO‐6‐HOC 5 H 3 N)Fe(CO) 2 (CH 3 CN) 2 ] + (BF 4 ) − with thiols or thiophenols in the presence of NEt 3 yielded 5‐coordinate iron thiolate complexes. Further derivation produced complexes [(2‐CH 2 CO‐6‐HOC 5 H 3 N)Fe(CO) 2 (SCH 2 CH 2 OH)] and [(2‐CH 2 CO‐6‐HOC 5 H 3 N)Fe(CO) 2 (CH 3 COO)], 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 HBF 4 ⋅Et 2 O, the solvated complex was regenerated by protonation of the thiolate ligands. The reactivity of several models with CO, isocyanide, cyanide, and H 2 was also investigated.