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Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes
Published on: April 1, 2013
Two-electron oxidation of N,N,N',N'-tetramethylphenylenediamine with a chromium(v) salen complex
Gezahegn Chaka1, Andreja Bakac
1Ames Laboratory, Iowa State University, Ames, IA 50011, USA.
Abstract:
The oxidation of tetramethylphenylenediamine (TMPD) with (salen)CrVO+ generates initially the 2-electron product TMPD2+, followed by the reaction with excess TMPD to yield the radical cation, TMPD+. The kinetics of both TMPD/(salen)CrVO+ and TMPD/TMPD2+ reactions are acid-dependent, with TMPD being the most reactive form, and the doubly protonated TMPDH2(2+) exhibiting no discernible reactivity toward either (salen)CrVO+ or TMPD2+. The specific rate constants for the individual reactions are: TMPD/(salen)CrVO+, k=(6.28+/-0.50)x10(9) M(-1) s(-1), TMPDH+/(salen)CrVO+, (3.89+/-0.31)x10(5), TMPD/TMPD2+, (7.61+/-0.42)x10(8), and TMPDH+/TMPD2+, (3.46+/-0.22)x10(4).
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