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Diferrous Cyanides as Models for the Fe-only Hydrogenases
The first systematic study of diferrous dicyano dithiolates is described. Oxidation of [Fe2(S2C2H4)(CN)2(CO)4]2- in the presence of cyanide and tertiary phosphines and of Fe2(S2C2H4)(CO)4(PMe3)2 in the presence of cyanide affords a series of diferrous cyanide derivatives that bear a stoichiometric,...
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Published in: | Journal of the American Chemical Society 2005-08, Vol.127 (31), p.11010-11018 |
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Main Authors: | , , , , , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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Summary: | The first systematic study of diferrous dicyano dithiolates is described. Oxidation of [Fe2(S2C2H4)(CN)2(CO)4]2- in the presence of cyanide and tertiary phosphines and of Fe2(S2C2H4)(CO)4(PMe3)2 in the presence of cyanide affords a series of diferrous cyanide derivatives that bear a stoichiometric, structural, and electronic relationship to the Hox air state of the Fe-only hydrogenases. With PPh3 as the trapping ligand, we obtained an unsymmetrical isomer of Fe2(S2C2H4)(μ-CO)(CN)2(PPh3)2(CO)2, as confirmed crystallographically. This diferrous cyanide features the semibridging CO-ligand, with Fe-μC bond lengths of 2.15 and 1.85 Å. Four isomers of Fe2(S2C2H4)(μ-CO)(CN)2(PMe3)2(CO)2 were observed, the initial product again being unsymmetrical but more stable isomers being symmetrical. DFT calculations confirm that the most stable isomers of Fe2(S2C2H4)(μ-CO)(CN)2(PMe3)2(CO)2 have cyanide trans to μ-CO. Oxidative decarbonylation also afforded the new tetracyanide [Fe2(S2C2H4)(μ-CO)(CN)4(CO)2]2-. Insights into the oxidative decarbonylation mechanism of these syntheses come from the spectroscopic characterization of the tetracarbonyl [Fe2(S2C2H4)(μ-CO)(CN)3(CO)3]-. This species reacts with PEt3 to produce the stable adduct [Fe2(S2C2H4)(μ-CO)(CN)3(CO)2(PEt3)]-. |
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ISSN: | 0002-7863 1520-5126 |
DOI: | 10.1021/ja051584d |