Mechanism of hydride transfer reaction from 4-(dimethylamino)phenyl methane derivatives to 2,3-dichloro-5,6-dicyano-p-benzoquinone

Shunzo Yamamoto, Tetsuo Sakurai, Liu Yingjin, Yoshimi Sueishi

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23 Citations (Scopus)

Abstract

The kinetics of the hydride-transfer reactions from bis[4- (dimethylamino)phenyl] methane (MH2), bis[4(dimethylamino)phenyl] methoxy methane (MHOMe), Leuco Malachite Green (MGH) and Leuco Crystal Violet (CVH) to 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) have been investigated spectrophotometrically by means of the stopped-flow technique. The negative activation enthalpies were obtained for the hydride-transfer reactions from MH2, MHOMe and MGH to DDQ in dichloromethane. These negative activation enthalpies suggest that the charge-transfer (CT) complexes are true intermediates in the hydride-transfer reactions from these donors to DDQ, as previously pointed out for MH2-DDQ system in trichloroethane. The formation of charge-transfer complexes between MH2, MHOMe, MGH and CVH and p-chloranil (CA) were observed in EPA (ethylether-pentane-ethanol) at low temperatures. The oxidation potential (E(ox)/°) of MHOMe, MGH and CVH were estimated using the linear correlation between the CT transition energy and the E(ox)/°value for the known CT complexes between CA and N,N-dimethylaniline derivatives. The rates were found to be correlated to the E(ox)/°values of the donors.

Original languageEnglish
Pages (from-to)833-837
Number of pages5
JournalPhysical Chemistry Chemical Physics
Volume1
Issue number5
DOIs
Publication statusPublished - Mar 1 1999

Fingerprint

Methane
quinones
Hydrides
hydrides
methane
Charge transfer
Derivatives
Chloranil
charge transfer
Enthalpy
enthalpy
Chemical activation
Trichloroethanes
activation
Gentian Violet
Methylene Chloride
pentanes
ethyl alcohol
Ethanol
benzoquinone

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Atomic and Molecular Physics, and Optics

Cite this

Mechanism of hydride transfer reaction from 4-(dimethylamino)phenyl methane derivatives to 2,3-dichloro-5,6-dicyano-p-benzoquinone. / Yamamoto, Shunzo; Sakurai, Tetsuo; Yingjin, Liu; Sueishi, Yoshimi.

In: Physical Chemistry Chemical Physics, Vol. 1, No. 5, 01.03.1999, p. 833-837.

Research output: Contribution to journalArticle

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