Responses of the Fe(CN)2(CO) Unit to Electronic Changes as Related to Its Role in [NiFe]Hydrogenase
| Autor: | Chia Huei Lai, Way Zen Lee, Matthew L. Miller, Joseph H. Reibenspies, Donald J. Darensbourg, Marcetta Y. Darensbourg |
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| Rok vydání: | 1998 |
| Předmět: | |
| Zdroj: | Journal of the American Chemical Society. 120:10103-10114 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/ja982053a |
| Popis: | The observation of nearly identical infrared spectra in the diatomic (2000 cm-1) region of oxidized forms of [NiFe]hydrogenases, as isolated from Chromatium vinosum (Happe et al. Nature 1997, 385, 126) and Desulfovibrio gigas (Volbeda et al. J. Am. Chem. Soc. 1996, 118, 12989) and the anion (η5-C5H5)Fe(CN)2(CO)- (Darensbourg et al. J. Am. Chem. Soc. 1997, 119, 7903), including isotopic label shifts, has prompted further development of the organometallic model complex as a spectroscopic reference. The vibrational spectroscopy of the pyramidal Fe(CN)2(CO) unit found in the salts of (η5-C5H5)Fe(CN)2(CO)- and (η5-C5Me5)Fe(CN)2(CO)- is thoroughly investigated with respect to band positions and intensity ratios as influenced by counterion and solvent. The neutral analogues (η5-C5H5)- and (η5-C5Me5)Fe(CN)(CO)2 as well as the protonated H[(η5-C5H5)Fe(CN)2(CO)] are included for comparison. The X-ray crystal structure of the latter finds short interionic N····N distances of 2.55 A indicative of CN-nitrogen protonat... |
| Databáze: | OpenAIRE |
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