Heteronuclear NMR Studies of Cobalt Corrinoids. 18. Correlation of Structure and Magnetic Resonance Parameters in Base-On Cobalamins(1).

Recent X-ray crystal structure determinations (including a new X-ray determination of the structure of cyano-13-epicobalamin reported herein) create a series of seven base-on cobalamins structurally characterized by modern crystallographic techniques in which the intramolecular equilibrium constant for coordination of the axial benzimidazole ligand (Bzm) varies from 76.6 to 4.90 x 10(7). For the five normal, unepimerized cobalamins, the free energy change for this equilibrium correlates linearly with the axial Co-N bond length (r(2) = 0.99). Absolute assignment of the (1)H and (13)C NMR spectra of two of these structurally characterized cobalamins (CH(3)Cbl and CN-13-epiCbl) together with literature assignments for the other complexes now provides reliable (13)C NMR assignments and chemical shifts for all seven complexes. The magnetic anisotropies of the central cobalt atom of all seven complexes, estimated by a method described earlier, are well correlated with the axial Co-N bond distance (r(2) = 0.97) and the free energy of coordination of the Bzm ligand (r(2) = 0.95). The (31)P NMR chemical shift of the phosphodiester moiety of the nucleotide loop is excellently correlated to the axial Co-N bond length (r(2) = 0.996) of the unepimerized cobalamins and provides a reliable method of estimating this bond length. The (15)N chemical shifts of the axially coordinated Bzm nitrogen vary strongly with the axial Co-N bond distance and correlate linearly with this structural parameter (r(2) = 0.991) except for the case of H(2)OCbl(+), which deviates substantially. However, there is a good linear correlation (r(2) = 0.98) of this (15)N chemical shift with the free energy of Bzm coordination for the five unepimerized cobalamins. Attempts to correlate (13)C NMR chemical shifts with structural, thermodynamic, and corrin ring conformational parameters are discussed.