Resonance Raman studies of the iron(II)-α-keto acid chromophore in model and enzyme complexes

R. Y.N. Ho, M. P. Mehn, E. L. Hegg, A. Liu, M. J. Ryle, R. P. Hausinger, L. Que

Research output: Contribution to journalArticlepeer-review

51 Scopus citations


The bidentate coordination of an α-keto acid to an iron(II) center via the keto group and the carboxylate gives rise to metal-to-ligand charge-transfer transitions between 400 and 600 nm in model complexes and in α-ketoglutarate-dependent dioxygenases. Excitation into these absorption bands of the Fe(II)TauD(α-KG) complex (TauD = taurine/α-ketoglutarate dioxygenase, α-KG = α-ketoglutarate) elicits two resonance Raman features at 460 and 1686 cm-1, both of which are sensitive to 18O labeling. Corresponding studies of model complexes, the six-coordinate [Fe(II)(6-Me3-TPA)(α-keto acid)]+ and the five-coordinate [Fe(II)(TpPh2)(α-keto acid)] (6-Me3-TPA = tris[(6-methyl-2-pyridyl)methyl]amine, TpPh2 = hydrotris(3,5-diphenylpyrazol-1-yl)borate), lead to the assignment of these two features to the Fe(II)(α-keto acid) chelate mode and the v(C=O) of the keto carbonyl group, respectively. Furthermore, the chelate mode is sensitive to the coordination number of the metal center; binding of a sixth ligand to the five-coordinate [Fe(II)(TpPh2)(benzoylformate)] elicits a 9-20 cm-1 downshift. Thus, the 10 cm-1 upshift of the chelate mode observed for Fe(II)TauD(α-KG) upon the addition of the substrate, taurine, is associated with the conversion of the six-coordinate metal center to a five-coordinate center, as observed for the iron center of clavaminate synthase from X-ray crystallography (Zhang, Z.; et al. Nat. Struct. Biol. 2000, 7, 127-133) and MCD studies (Zhou, J.; et al. J. Am. Chem. Soc. 1998, 120, 13539-13540). These studies provide useful insights into the initial steps of the oxygen activation mechanism of α-ketoglutarate-dependent dioxygenases.

Original languageEnglish (US)
Pages (from-to)5022-5029
Number of pages8
JournalJournal of the American Chemical Society
Issue number21
StatePublished - 2001


Dive into the research topics of 'Resonance Raman studies of the iron(II)-α-keto acid chromophore in model and enzyme complexes'. Together they form a unique fingerprint.

Cite this