期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 20, 期 6, 页码 1677-1682出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201304290
关键词
carbonyl complexes; enzyme models; hydrogenases; iron; thiolates
资金
- National Natural Science Foundation of China [21242012, 21201049, 21302028]
- Harbin Science and Technology Bureau [2013RFLXJ002]
- Fundamental Research Funds for the Central Universities [HIT. NSRIF. 2013042]
- Swiss National Science Foundation [200020_134473/1]
- Swiss National Science Foundation (SNF) [200020_134473] Funding Source: Swiss National Science Foundation (SNF)
[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 center dot Et2O, 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.
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