RESONANCE RAMAN-SPECTRA, EXCITATION PROFILES AND EXCITED (IRON-]PYRIDINE CHARGE-TRANSFER) STATE GEOMETRY OF BISPYRIDINE IRON(II) HEME

被引：84

作者：

WRIGHT, PG ^{[1
]}

STEIN, P ^{[1
]}

BURKE, JM ^{[1
]}

SPIRO, TG ^{[1
]}

机构：

[1] PRINCETON UNIV,DEPT CHEM,PRINCETON,NJ 08540

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1979年 / 101卷 / 13期

关键词：

D O I：

10.1021/ja00507a018

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Totally symmetric bound pyridine vibrational modes are observed in the resonance Raman spectra of (py)2Fe11MP (py = pyridine, MP = mesoporphyrin IX dimethyl ester) and the pyridine-rfs analogue. The frequencies and their deuterium shifts are satisfactorily calculated using a benzene force field and an Fe-N stretching force constant of 1.96 mdyn Å-1. The Fe-py stretching mode is at 179 cm-1. Excitation profiles show all py modes maximizing at 496.5 nm, close to a bump in the absorption spectrum at 490 nm. Approximate origin shifts are obtained from the relative Raman intensities of the py modes and are combined with the calculated eigenvectors to provide a qualitative picture of the geometry in the resonant excited state, which is assigned to dπ(Fe)→π*(py) charge transfer. Copyright © 1979, American Chemical Society. All rights reserved.

引用

页码：3531 / 3535

页数：5

共 24 条

[1] RESONANCE RAMAN-SPECTRA OF METHEMOGLOBIN DERIVATIVES - SELECTIVE ENHANCEMENT OF AXIAL LIGAND VIBRATIONS AND LACK OF AN EFFECT OF INOSITOL HEXAPHOSPHATE [J].