REACTIONS OF THE IRON(III) TETRAPHENYLPORPHYRIN-PI CATION RADICAL WITH TRIPHENYLPHOSPHINE AND THE NITRITE ANION - FORMATION OF BETA-SUBSTITUTED IRON(III) PORPHYRINS

被引:33
作者
MALEK, A
LATOSGRAZYNSKI, L
BARTCZAK, TJ
ZADLO, A
机构
[1] WROCLAW B BEIRUT UNIV,INST CHEM,14 F JOLIOT CURIE ST,PL-50383 WROCLAW,POLAND
[2] TECH UNIV LODZ,INST GEN CHEM,PL-90924 LODZ,POLAND
关键词
D O I
10.1021/ic00016a021
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The formation of iron(III) beta-(triphenylphosphonio)tetraphenylporphyrin (beta-PPh3+-TPP)Fe(III) and iron(III) beta-nitrotetraphenylporphyrin (beta-NO2-TPP)Fe(III) in the reaction of iron(III) tetraphenylporphyrin cation radical (TPP.)Fe(III)(ClO4(0)2 with triphenylphosphine or nitrite anion has been established through a variety of spectroscopic investigations. The reaction mechanism seems to be analogous to that elucidated for a variety of metalloporphyrin cation radicals or arene cation radicals. The structure of (beta-PPh3+-TPP)Fe(III)Cl2.CHCl3, C63H43N4Cl5PFe, has been determined at 173 K by X-ray diffraction: monoclinic space group I2/a, Z = 8, a = 27.948 (3) angstrom, b = 11.286 (3) angstrom, c = 33.633 (5) angstrom, beta = 94.31 (1)-degrees, least-squares refinement of parameters using 3658 reflections (Mo K-alpha) yielding R = 0.091, R(W) = 0.06. The structural study of (beta-PPh3+-TPP)Fe(III)Cl2 revealed its "zwitterionic" nature. The species belongs to a rather small class of high-spin six-coordinate iron(III) porphyrins and is the first example where two apical positions are occupied by chloride anions. The Fe-Cl distances are Fe-Cl(1) = 2.429(3) angstrom and Fe-Cl(2) = 2.348 (3) angstrom. The iron atom is precisely located in the plane of an expanded porphyrin core of a saddlelike conformation with mean Fe-N = 2.055 (7) A. This value is in the range of Fe-N distances found in other known high-spin ferric porphyrins. This geometry is also preserved in chloroform and has been established for bromide and iodide axial ligands. The proton NMR spectra of high-spin and low-spin iron(III) beta-substituted porphyrins have been obtained and analyzed. Functional group assignments have been made with the use of selective deuteration and methyl substitution. The pattern of seven pyrrole resonances reflects the asymmetry that results from beta-substitution. This pattern is diagnostic for mono-beta-substitution. Because of hindrance of the phenyl group, rotation around the pyrrole carbon-phosphorus bond is restricted.
引用
收藏
页码:3222 / 3230
页数:9
相关论文
共 77 条
[51]   PROTON NUCLEAR MAGNETIC-RESONANCE AND ELECTRON-SPIN RESONANCE INVESTIGATION OF ELECTRONIC-STRUCTURE AND MAGNETIC PROPERTIES OF SYNTHETIC LOW-SPIN FERRIC PORPHYRINS [J].
LAMAR, GN ;
WALKER, FA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (06) :1782-1790
[52]   PROTON NUCLEAR MAGNETIC-RESONANCE CHARACTERIZATION OF THE ELECTRONIC-STRUCTURE OF HORSERADISH-PEROXIDASE COMPOUND-I [J].
LAMAR, GN ;
ROPP, JSD .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (01) :395-397
[53]  
LAMAR GN, 1979, PORPHYRINS, V4, P61, DOI DOI 10.1016/B978-0-12-220104-2.50009-0
[54]   ROTHEMUND AND ADLER-LONGO REACTIONS REVISITED - SYNTHESIS OF TETRAPHENYLPORPHYRINS UNDER EQUILIBRIUM CONDITIONS [J].
LINDSEY, JS ;
SCHREIMAN, IC ;
HSU, HC ;
KEARNEY, PC ;
MARGUERETTAZ, AM .
JOURNAL OF ORGANIC CHEMISTRY, 1987, 52 (05) :827-836
[55]   IRON PORPHYRIN NITRENE COMPLEXES - PREPARATION, PROPERTIES, AND CRYSTAL-STRUCTURE OF PORPHYRIN IRON(III) COMPLEXES WITH A TOSYLNITRENE INSERTED INTO AN FE-N BOND [J].
MAHY, JP ;
BATTIONI, P ;
BEDI, G ;
MANSUY, D ;
FISCHER, J ;
WEISS, R ;
MORGENSTERNBADARAU, I .
INORGANIC CHEMISTRY, 1988, 27 (02) :353-359
[56]   6 COORDINATION IN HIGH-SPIN FERRIC PORPHYRINS - NEW STRUCTURAL TYPE AND MODELS FOR AQUOMETHEMOGLOBIN [J].
MASHIKO, T ;
KASTNER, ME ;
SPARTALIAN, K ;
SCHEIDT, WR ;
REED, CA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (20) :6354-6362
[57]   DIRECT OBSERVATION OF THE KINETIC ACIDITIES OF TRANSIENT AROMATIC CATION RADICALS - THE MECHANISM OF ELECTROPHILIC SIDE-CHAIN NITRATION OF THE METHYLBENZENES [J].
MASNOVI, JM ;
SANKARARAMAN, S ;
KOCHI, JK .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (06) :2263-2276
[58]  
MCMURRY JT, CYTOCHROME P450 STRU, P1
[59]   THE ONE-ELECTRON OXIDATION OF PORPHYRINS TO PORPHYRIN PI-CATION RADICALS BY PEROXIDASES - AN ELECTRON-SPIN RESONANCE INVESTIGATION [J].
MOREHOUSE, KM ;
SIPE, HJ ;
MASON, RP .
ARCHIVES OF BIOCHEMISTRY AND BIOPHYSICS, 1989, 273 (01) :158-164
[60]  
MORISHIMA I, 1980, J AM CHEM SOC, V102, P2429, DOI 10.1021/ja00527a047