Kinetics of Linkage Isomerization of (5-Methyltetrazolato)pentaamminecobalt(III)

William L. Purcell

Research output: Contribution to journalArticlepeer-review

26 Scopus citations

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 (US)
Pages (from-to)1205-1208
Number of pages4
JournalInorganic Chemistry
Volume22
Issue number8
DOIs
StatePublished - Apr 1983

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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