PREPARATION AND CHARACTERIZATION OF OXOIRON(IV) CHLORIN COMPLEXES AS THE 1ST MODELS FOR A REACTION INTERMEDIATE IN THE CATALYTIC CYCLE OF CYTOCHROME-D

被引:27
作者
OZAWA, S
WATANABE, Y
NAKASHIMA, S
KITAGAWA, T
MORISHIMA, I
机构
[1] KYOTO UNIV,GRAD SCH ENGN,DIV MOLEC ENGN,KYOTO 60601,JAPAN
[2] INST MOLEC SCI,OKAZAKI NATL RES INST,OKAZAKI,AICHI 444,JAPAN
关键词
D O I
10.1021/ja00081a026
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
As models for a reaction intermediate in the catalytic cycle of cytochrome d, two types of oxoferryl chlorin complexes, (TPC)Fe(IV)O(N-MeIm) and (TPC)Fe(IV)O (TPC = tetraphenylchlorin, N-MeIm = N-methylimidazole), have been prepared for the first time by an autoxidation reaction of (TPC)Fe(II) with O2. Oxyiron(II)(TPC) and mu-peroxo-bridged iron(III) dimer, (TPC)Fe(III)OOFe(III)(TPC), are also detected in the course of the reaction. The six-coordinated (TPC)Fe(IV)O(N-MeIm) complex is produced by adding N-methylimidazole to the mu-peroxo-bridged iron(III) chlorin dimer at -80-degrees-C. The mu-peroxo-bridged iron(III) dimer, the formation of which has been confirmed by paramagnetic NMR, undergoes homolytic cleavage of the O-O bond upon laser illumination to yield the five-coordinated (TPC)Fe(IV)O complex. The absorption spectrum of (TPC)Fe(IV)O(N-MeIm) shows a characteristic red-shifted band at 630 nm as observed in the case of the oxoferryl intermediate of cytochrome d. Proton NMR spectra of (TPC)Fe(IV)O(N-MeIm) exhibit a small hyperfine shift of the pyrrole protons, consistent with the oxoferryl formulation. However, the paramagnetic NMR resonances of the saturated pyrrole (pyrroline) ring protons show unusual splitting into upfield and downfield region, suggesting deformation of the pyrroline ring of the chlorin complex. While the unusually high frequency of nu(Fe(IV)=O) (815 cm-1) and large isotopic shift (DELTAnu = 46 cm-1) observed for the oxoferryl intermediate of cytochrome d have been attributed to the chlorin macrocycle (heme d), the five- and six-coordinated oxoferryl chlorin complexes reported here exhibit nu(Fe(IV)=O) frequencies and iotopic (O-16/O-18) frequency shifts nearly identical to those of the corresponding porphyrin complexes, respectively.
引用
收藏
页码:634 / 641
页数:8
相关论文
共 62 条
[1]   RESONANCE RAMAN-SPECTROSCOPY OF METALLOCHLORINS .2. PROPERTIES OF MESOSUBSTITUTED SYSTEMS [J].
ANDERSSON, LA ;
LOEHR, TM ;
SOTIRIOU, C ;
WU, W ;
CHANG, CK .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (11) :2908-2916
[2]   INFLUENCE OF SYMMETRY ON THE VIBRATIONAL-SPECTRA OF ZN(TPP), ZN(TPC), AND ZN(TPIBC) [J].
ANDERSSON, LA ;
LOEHR, TM ;
THOMPSON, RG ;
STRAUSS, SH .
INORGANIC CHEMISTRY, 1990, 29 (11) :2142-2147
[3]   RESONANCE RAMAN-SPECTROSCOPY OF METALLOCHLORINS - MODELS FOR GREEN HEME PROTEIN PROSTHETIC GROUPS [J].
ANDERSSON, LA ;
LOEHR, TM ;
CHANG, CK ;
MAUK, AG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (01) :182-191
[4]   FACILE LACTONIZATION AND INVERSION OF VICINAL DIOLS IN HEME D-TYPE CHLORINS - A SPECTROSCOPIC STUDY [J].
ANDERSSON, LA ;
SOTIRIOU, C ;
CHANG, CK ;
LOEHR, TM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (01) :258-264
[5]   THE AEROBIC RESPIRATORY-CHAIN OF ESCHERICHIA-COLI [J].
ANRAKU, Y ;
GENNIS, RB .
TRENDS IN BIOCHEMICAL SCIENCES, 1987, 12 (07) :262-266
[6]   FORMATION OF FERRYLTETRAPHENYLPORPHYRIN BY LASER IRRADIATION [J].
BAJDOR, K ;
NAKAMOTO, K .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (10) :3045-3046
[7]   NUCLEAR MAGNETIC-RESONANCE STUDIES OF AXIAL AMINE COORDINATION IN SYNTHETIC FERRYL, (FEIVO)2+, PORPHYRIN COMPLEXES AND IN FERRYL MYOGLOBIN [J].
BALCH, AL ;
LAMAR, GN ;
LATOSGRAZYNSKI, L ;
RENNER, MW ;
THANABAL, V .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (11) :3003-3007
[8]  
BALCH AL, 1984, J AM CHEM SOC, V106, P7779, DOI 10.1021/ja00337a022
[9]   RESONANCE RAMAN STUDIES OF MONOMERIC AND OXYGEN-BRIDGED DIMERIC IRON OCTETHYLCHLORIN [J].
BOLDT, NJ ;
BOCIAN, DF .
JOURNAL OF PHYSICAL CHEMISTRY, 1988, 92 (03) :581-586
[10]   KINETICS OF THE REACTIONS OF TRIOXODINITRATE AND NITRITE IONS WITH CYTOCHROME-D IN ESCHERICHIA-COLI [J].
BONNER, FT ;
HUGHES, MN ;
POOLE, RK ;
SCOTT, RI .
BIOCHIMICA ET BIOPHYSICA ACTA, 1991, 1056 (02) :133-138