The effect of counter cations on second-order asymmetric transformations in fac-Δ- and Λ-tris(R-cysteinato-N,S)cobaltate(III) complexes and the kinetics of mutarotation

Masakazu Kita, Kazuaki Yamanari

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Abstract

A rapid reversible inversion (epimerization) between the Δ-(R,R,R) and Λ-(R,R,R) diastereomers for fac-Δ- and Λ-tris(R-cysteinato-N,S)cobaltate(III) occurs at room temperature in an aqueous solution of each salt. The half-lives for the mutarotation were measured (k = kΛ + kΔ): 80 and 6 minutes at 20 and 40°C, respectively. The equilibrium constants, K = [Λ-(R,R,R)]/[Δ(R,R,R)], are 1.2 at 20°C and 1.0 at 40°C, which means that the cobalt inversion rate constant kΛ nearly equals kΔ. Eight kinds of metal salts, M3[Co(R-cys-N,S)3] [M = Li+, Na+, K+, Rb+, Cs+; M1/2 = Ca2+, Sr2+, Ba2+], were prepared. It was found that all these salts show a second-order asymmetric transformation under a solid-solution equilibrium at room temperature of the kind first demonstrated for the Ba2+ salt by Arnold and Jackson. The phenomenon led to the Δ-(R,R,R) diastereomer for the salts of Li+, Na+, K+, Rb+, Cs+, Ca2+ and Sr2+, but to the Λ-(R,R,R) diastereomer for Ba2+. These results could be clearly explained by solubility measurements of each diastereomeric salt pair.

Original languageEnglish
Pages (from-to)1221-1226
Number of pages6
JournalJournal of the Chemical Society, Dalton Transactions
Issue number8
Publication statusPublished - Apr 21 1999
Externally publishedYes

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Cations
Salts
Kinetics
Equilibrium constants
Cobalt
Solid solutions
Rate constants
Solubility
Metals
Temperature

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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title = "The effect of counter cations on second-order asymmetric transformations in fac-Δ- and Λ-tris(R-cysteinato-N,S)cobaltate(III) complexes and the kinetics of mutarotation",
abstract = "A rapid reversible inversion (epimerization) between the Δ-(R,R,R) and Λ-(R,R,R) diastereomers for fac-Δ- and Λ-tris(R-cysteinato-N,S)cobaltate(III) occurs at room temperature in an aqueous solution of each salt. The half-lives for the mutarotation were measured (k = kΛ + kΔ): 80 and 6 minutes at 20 and 40°C, respectively. The equilibrium constants, K = [Λ-(R,R,R)]/[Δ(R,R,R)], are 1.2 at 20°C and 1.0 at 40°C, which means that the cobalt inversion rate constant kΛ nearly equals kΔ. Eight kinds of metal salts, M3[Co(R-cys-N,S)3] [M = Li+, Na+, K+, Rb+, Cs+; M1/2 = Ca2+, Sr2+, Ba2+], were prepared. It was found that all these salts show a second-order asymmetric transformation under a solid-solution equilibrium at room temperature of the kind first demonstrated for the Ba2+ salt by Arnold and Jackson. The phenomenon led to the Δ-(R,R,R) diastereomer for the salts of Li+, Na+, K+, Rb+, Cs+, Ca2+ and Sr2+, but to the Λ-(R,R,R) diastereomer for Ba2+. These results could be clearly explained by solubility measurements of each diastereomeric salt pair.",
author = "Masakazu Kita and Kazuaki Yamanari",
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