Two-electron oxidation of N,N,N′,N′-tetramethylphenylenediamine with a chromium(V) salen complex

被引：9

作者：

Chaka, Gezahegn ^{[1
]}

Bakac, Andreja ^{[1
]}

机构：

[1] Iowa State Univ, Ames Lab, Ames, IA 50011 USA

来源：

DALTON TRANSACTIONS | 2009年 / 02期

关键词：

PHOTOINDUCED ELECTRON-TRANSFER; OXOCHROMIUM(V) CATIONS; MOLECULAR-STRUCTURE; DIFFERENT OXIDANTS; CRYSTAL-STRUCTURE; AROMATIC-AMINES; IONS; N; N'; N'-TETRAMETHYL-P-PHENYLENEDIAMINE; IONIZATION; GENERATION;

D O I：

10.1039/b811140e

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The oxidation of tetramethylphenylenediamine (TMPD) with (salen) (CrO+)-O-V generates initially the 2-electron product TMPD2+, followed by the reaction with excess TMPD to yield the radical cation, TMPD center dot+. The kinetics of both TMPD/(salen) (CrO+)-O-V and TMPD/TMPD2+ reactions are acid-dependent, with TMPD being the most reactive form, and the doubly protonated TMPDH22+ exhibiting no discernible reactivity toward either (salen) (CrO+)-O-V or TMPD2+. The specific rate constants for the individual reactions are: TMPD/(salen) (CrO+)-O-V, k = (6.28 +/- 0.50) x 10(9) M-1 s(-1), TMPDH+/(salen) CrVO+, (3.89 +/- 0.31) x 10(5), TMPD/TMPD2+, (7.61 +/- 0.42) x 10(8), and TMPDH+/TMPD2+, (3.46 +/- 0.22) x 10(4).

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页码：318 / 321

页数：4

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