The electronic and vibrational structures of iron-oxo porphyrin with a methoxide or cysteinate axial ligand.
作者： Takehiro Ohta , Koji Matsuura , Kazunari Yoshizawa , Isao Morishima
DOI: 10.1016/S0162-0134(00)00162-8
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摘要: Hybrid density functional theory (DFT) calculations for the electronic and vibrational structures of compound I species with a methoxide (MeO-) (1) or cysteinate (CysS-) (2) axial ligand are carried out in order to elucidate natures methoxide-coordinating new type (Bull. Chem. Soc. Jpn. 71 (1998) 1343) cysteinate-coordinating chloroperoxidase (CPO-I) cytochrome P450s (P450-I). DFT computations 1 2 demonstrate that these "anionic" ligands spin carrier; 70% (80%) resides on O (S) atom 30% (20%) is distributed porphyrin ring. These results suggest generation species, one electron removed from iron centers rest supplied oxidizable instead Vibrational analyses Fe=O bond more strongly activated compared stretching mode at 849 cm(-1) (878 cm(-1)) doublet state1a (2a) 814 (875 quartet state 1b (2b). This reverse strength respect donor should have relevance significantly oxidized character CysS- ligand. In conjunction recent extensive resonance Raman (RR) studies, some interpretations unsettled RR synthetic [O=FeIV(TMP*+)(alcohol)] (J. Am. 113 (1991) 6542) concerning O=Fe frequencies discussed.
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