Mechanistic information from pressure acceleration of hydride formation via proton binding to a cobalt(I) macrocycle

Etsuko Fujita, James F. Wishart, Rudi Van Eldik

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

The effect of pressure on proton binding to the racemic isomer of the cobalt(I) macrocycle, CoL+ (L = 5,7,7,12.-14, 14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene), has been studied for a series of proton donors using pulse radiolysis techniques. The second-order rate constants for the reaction of CoL+ with proton donors decrease with increasing pKa of the donor acid, consistent with a reaction occurring via proton transfer. Whereas the corresponding volumes of activation (ΔV‡) are rather small and negative for all acids (proton donors) with pKa values below 8.5, significantly larger negative activation volumes are found for weaker acids (pKa> 9.5) containing OH groups as proton donors. In the latter case, the observed ΔV‡ for these protonation reactions show a correlation with the reaction volumes (ΔV°ion) for the ionization of the weak acids with a slope of 0.44, indicating that bond dissociation of the weak acid molecule bound to the metal center proceeds approximately halfway at the transition state along the reaction coordinate in terms of volume changes.

Original languageEnglish
Pages (from-to)1579-1583
Number of pages5
JournalInorganic Chemistry
Volume41
Issue number6
DOIs
Publication statusPublished - Mar 25 2002

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Cobalt
Hydrides
hydrides
Protons
cobalt
Acids
protons
acids
Chemical activation
Radiolysis
Proton transfer
activation
Protonation
Isomers
Ionization
dienes
Rate constants
radiolysis
Metals
isomers

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Mechanistic information from pressure acceleration of hydride formation via proton binding to a cobalt(I) macrocycle. / Fujita, Etsuko; Wishart, James F.; Van Eldik, Rudi.

In: Inorganic Chemistry, Vol. 41, No. 6, 25.03.2002, p. 1579-1583.

Research output: Contribution to journalArticle

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AB - The effect of pressure on proton binding to the racemic isomer of the cobalt(I) macrocycle, CoL+ (L = 5,7,7,12.-14, 14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene), has been studied for a series of proton donors using pulse radiolysis techniques. The second-order rate constants for the reaction of CoL+ with proton donors decrease with increasing pKa of the donor acid, consistent with a reaction occurring via proton transfer. Whereas the corresponding volumes of activation (ΔV‡) are rather small and negative for all acids (proton donors) with pKa values below 8.5, significantly larger negative activation volumes are found for weaker acids (pKa> 9.5) containing OH groups as proton donors. In the latter case, the observed ΔV‡ for these protonation reactions show a correlation with the reaction volumes (ΔV°ion) for the ionization of the weak acids with a slope of 0.44, indicating that bond dissociation of the weak acid molecule bound to the metal center proceeds approximately halfway at the transition state along the reaction coordinate in terms of volume changes.

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