Kinetics of linkage isomerization of (5-methyltetrazolato)pentaamminecobalt(III)

William L. Purcell

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Abstract

The kinetics of the linkage isomerization reaction for N1-bonded (5-methyltetrazolato)pentaamminecobalt(III) rearranging to the N2-bonded complex has been studied as a function of temperature and pH. Rate constants for isomerization of the protonated (3+) complex and deprotonated (2+) complex were found to differ appreciably, and a base-catalyzed pathway for the 2+ complex was found. At 25°C and ionic strength 1.0 M, k3+ = (3.1 ± 2.5) × 10-4 s-1 and k2+ = (1.9 ± 0.5) × 10-6 s-1. Activation parameters for the two processes are Δ3+ = 15 ± 4 kcal mol-1, ΔS3+ = -24 ± 13 cal K-1 mol-1, Δ2+ = 26.0 ± 1.8 kcal mol-1, and ΔS2+ = 2.5 ± 5.6 cal K-1 mol-1. At 41.2°C in basic media, kobsd = k2+ + kOH[OH-] where kOH = (3.1 ± 0.7) × 10-3 M-1 s-1.

Original languageEnglish
Pages (from-to)1205-1208
Number of pages4
JournalInorganic Chemistry
Volume22
Issue number8
StatePublished - Dec 1 1983

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Isomerization
linkages
isomerization
Kinetics
kinetics
Ionic strength
Rate constants
Chemical activation
activation
Temperature
temperature
hydroxide ion

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Kinetics of linkage isomerization of (5-methyltetrazolato)pentaamminecobalt(III). / Purcell, William L.

In: Inorganic Chemistry, Vol. 22, No. 8, 01.12.1983, p. 1205-1208.

Research output: Contribution to journalArticle

Purcell, William L. / Kinetics of linkage isomerization of (5-methyltetrazolato)pentaamminecobalt(III). In: Inorganic Chemistry. 1983 ; Vol. 22, No. 8. pp. 1205-1208.
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N2 - The kinetics of the linkage isomerization reaction for N1-bonded (5-methyltetrazolato)pentaamminecobalt(III) rearranging to the N2-bonded complex has been studied as a function of temperature and pH. Rate constants for isomerization of the protonated (3+) complex and deprotonated (2+) complex were found to differ appreciably, and a base-catalyzed pathway for the 2+ complex was found. At 25°C and ionic strength 1.0 M, k3+ = (3.1 ± 2.5) × 10-4 s-1 and k2+ = (1.9 ± 0.5) × 10-6 s-1. Activation parameters for the two processes are Δ3+‡ = 15 ± 4 kcal mol-1, ΔS3+‡ = -24 ± 13 cal K-1 mol-1, Δ2+‡ = 26.0 ± 1.8 kcal mol-1, and ΔS2+‡ = 2.5 ± 5.6 cal K-1 mol-1. At 41.2°C in basic media, kobsd = k2+ + kOH[OH-] where kOH = (3.1 ± 0.7) × 10-3 M-1 s-1.

AB - The kinetics of the linkage isomerization reaction for N1-bonded (5-methyltetrazolato)pentaamminecobalt(III) rearranging to the N2-bonded complex has been studied as a function of temperature and pH. Rate constants for isomerization of the protonated (3+) complex and deprotonated (2+) complex were found to differ appreciably, and a base-catalyzed pathway for the 2+ complex was found. At 25°C and ionic strength 1.0 M, k3+ = (3.1 ± 2.5) × 10-4 s-1 and k2+ = (1.9 ± 0.5) × 10-6 s-1. Activation parameters for the two processes are Δ3+‡ = 15 ± 4 kcal mol-1, ΔS3+‡ = -24 ± 13 cal K-1 mol-1, Δ2+‡ = 26.0 ± 1.8 kcal mol-1, and ΔS2+‡ = 2.5 ± 5.6 cal K-1 mol-1. At 41.2°C in basic media, kobsd = k2+ + kOH[OH-] where kOH = (3.1 ± 0.7) × 10-3 M-1 s-1.

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