ic401715e_si_002.cif (38.49 kB)
Trans and Cis Effects of Axial Fluoroalkyl Ligands in Vitamin B12 Analogues: Relationship between Alkyl- and Fluoroalkyl-Cobalamins
dataset
posted on 2013-12-02, 00:00 authored by Lucio Randaccio, Giovanna Brancatelli, Nicola Demitri, Renata Dreos, Neal Hickey, Patrizia Siega, Silvano GeremiaCF2HCbl,
CF3Cbl , and CF3CH2Cbl have been synthesized and characterized in solution by 1H NMR and UV–vis spectroscopy, and their X-ray crystal
structures have been determined using synchrotron radiation. The structure
of CF3CH2Cbl is reported for the
first time, whereas those of CF2HCbl and CF3Cbl are re-examined to obtain more precise structural
data. Comparison of the structural data obtained with the alkylcobalamin
analogues, MeCbl and EtCbl, indicates that the Co–C and Co–NB3
bond lengths are shorter in the fluoroalkylcobalamins. The structural
data of the fluoroalkylcobalamins previously reported in the literature
had been conflicting in this regard. Thus, a much less dramatic shortening
of the two axial bonds was found for CF3Cbl, whereas in the case of CF2HCbl, the Co–NB3
bond length is shorter than in MeCbl. Direct comparison of the structures
of CF3CH2Cbl and EtCbl indicates
a large distortion of the axial fragment in the former case that can
be attributed to steric effects. A number of previously reported correlations
of the effect of the β-ligand on the structure and properties
of cobalamins are re-examined in light of the present results. Particular
emphasis is placed on the axial fragment. This analysis substantially
confirms and, with the new data reported here, adjusts and expands
the data set for correlations between trans and cis influences of
the β-ligand of cobalamins and their structure (Co–X
and Co–NB3 distances and corrin fold angle) and properties
(UV–vis spectra, NMR spectra, and pKbase‑off).