The Ligand Substitution Reactions of Hydrophobic Vitamin B12 Derivatives. Reaction of Cobyric Acid Heptapropyl Ester with Heterocyclic N-donor Ligands

  • MSA Hamza
  • MA Elawady
  • HM Marques
Keywords: Hydrophobic vitamin B12, cobalt corrinoids, equilibrium constants, solvent polarity, trans influence

Abstract

The hydrophobic cobyrinic acid heptapropyl ester corrinoids XCbs-Pr (axial ligand X=CN, SO32–, CH3 and CH3CH2) have been prepared from vitamin B12 by hydrolysis of the amide side chains and their conversion to propyl esters. Both the position of the γ-band and the general shape of the UV-visible spectra of these complexes show significant solvent dependence as the polarity of the solvent is varied. The equilibrium constants, K, for the reaction of five-membered heterocyclic nitrogenous bases (the azoles imidazole, pyrazole and 1,2,4-triazole) with displacement of coordinated H2O in aquacyanocobyrinic acid heptapropyl ester, and coordination by the predominantly five-coordinate complexes sulphitocobyrinic acid heptapropyl ester, ethylcobyrinic acid heptapropyl ester and methylcobyrinic acid heptapropyl ester, have been determined spectrophotometrically at 25 °C in water, methanol, acetonitrile, ethyl acetate and toluene. Values of K are dependent on the identity of the trans ligand (X=CN>SO2–> CH3 > CH3CH2 ); they increase with the basicity of the azole (pyrazole < 1,2,4-triazole < imidazole); and they increase as the solvent polarity increases (toluene<ethyl acetate< acetonitrile< methanol< H2O). Molecular mechanics calculations suggest that these effects are largely electronic in origin.

Keywords: Hydrophobic vitamin B12, cobalt corrinoids, equilibrium constants, solvent polarity, trans influence

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Published
2015-10-07
Section
Articles

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eISSN: 0379-4350