OXYGEN-TRANSFER FROM PH(4)PHSO(5) TO MANGANESE PORPHYRINS - KINETICS AND MECHANISM OF THE FORMATION OF THE OXO SPECIES IN HOMOGENEOUS SOLUTION

被引：29

作者：

CAMPESTRINI, S ^{[1
]}

DIFURIA, F ^{[1
]}

LABAT, G ^{[1
]}

NOVELLO, F ^{[1
]}

机构：

[1] UNIV PADUA,CNR,CTR STUDIO MECCANISMI REAZ ORGAN,DIPARTIMENTO CHIM ORGAN,I-35131 PADUA,ITALY

来源：

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 | 1994年 / 10期

关键词：

D O I：

10.1039/p29940002175

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The kinetics and mechanism of the oxygenation of Mn(TMP)Cl, Mn(TDCPP)Cl and Mn(Br(8)TMP)Cl by Ph(4)PhSO(5) has been investigated in 1.2-dichloroethane and acetonitrile. In both solvents the reaction takes place only in the presence of species acting as axial ligands. of the manganese porphyrins, e.g. imidazole or 4-tert-butylpyridine whose association constants to the metal have: been measured. The rates of disappearance of the manganese porphyrin and of the appearance of the oxo-species, obtained by the stopped-flow, technique, are identical within the experimental error. This finding, together with the determination of the kinetic law of the reaction allows us to suggest that the oxygen transfer process may be a simple bimolecular reaction or that, if an intermediate is formed, it is rather short lived.

引用

页码：2175 / 2180

页数：6

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