Spin transition in a manganese(III) porphyrin cation radical, its transformation to a dichloromanganese(IV) porphyrin, and chlorination of hydrocarbons by the latter

被引:44
作者
Kaustov, L
Tal, ME
Shames, AI
Gross, Z
机构
[1] TECHNION ISRAEL INST TECHNOL,DEPT CHEM,IL-32000 HAIFA,ISRAEL
[2] BEN GURION UNIV NEGEV,DEPT PHYS,LAB MAGNET RESONANCE,IL-84105 BEER SHEVA,ISRAEL
关键词
D O I
10.1021/ic961207p
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Chemical oxidation of (TMP)Mn-III(Cl) (TMP = the tetramesitylporphyrinato dianion) by Fe(ClO4)(3) leads to the porphyrin-oxidized product (TMP.+)Mn-III(ClO4)(2). Magnetic measurements and EPR spectroscopy show that the total spin of the complex changes from S = 5/2 at high temperature to S = 3/2 at low temperature. Ligand exchange of the perchlorato ligands in (TMP.+)Mn-III(ClO4)(2) by chloride anions is accompanied by a change of the oxidation site from porphyrin to metal, resulting in (TMP)Mn-IV(Cl)(2). This high-valent-metal complex can effect chlorine atom transfer to olefins, as well as to dimedone and chlorodimedone, natural substrates of chloroperoxidases.
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页码:3503 / 3511
页数:9
相关论文
共 88 条
[1]  
Alder A. D., 1970, J INORG NUCL CHEM, V32, P2443
[2]   REACTION OF HYDROXIDE ION WITH MANGANESE(III) TETRAMESITYLPORPHYRIN AND THE OXIDATION-STATES OF MANGANESE TETRAMESITYLPORPHYRINS [J].
ARASASINGHAM, RD ;
BRUICE, TC .
INORGANIC CHEMISTRY, 1990, 29 (07) :1422-1427
[3]  
AYOUGOU K, 1995, ANGEW CHEM INT EDIT, V34, P343
[4]  
AYOUGOU K, 1995, ANGEW CHEM, V107, P370
[5]   OXIDATION OF RED FERRYL [(FEIVO)2+]PORPHYRIN COMPLEXES TO GREEN FERRYL [(FEIVO)2+]PORPHYRIN RADICAL COMPLEXES [J].
BALCH, AL ;
LATOSGRAZYNSKI, L ;
RENNER, MW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (10) :2983-2985
[6]  
BALCH AL, 1984, J AM CHEM SOC, V106, P7779, DOI 10.1021/ja00337a022
[7]   SYNTHESIS AND REMARKABLE PROPERTIES OF IRON BETA-POLYNITROPORPHYRINS AS CATALYSTS FOR MONOOXYGENATION REACTIONS [J].
BARTOLI, JF ;
BATTIONI, P ;
DEFOOR, WR ;
MANSUY, D .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1994, (01) :23-24
[8]  
BARZILAY CM, 1995, Z CHEM EUR J, V1, P312
[9]  
BECKWITH JR, 1963, J BIOL CHEM, V238, P3091
[10]   OXOIRON(IV) PORPHYRINS DERIVED FROM CHARGED IRON(III) TETRAARYLPORPHYRINS AND CHEMICAL OXIDANTS IN AQUEOUS AND METHANOLIC SOLUTIONS [J].
BELL, SEJ ;
COOKE, PR ;
INCHLEY, P ;
LEANORD, DR ;
SMITH, JRL ;
ROBBINS, A .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1991, (04) :549-559