Abstract
In the crystals of some cobaloxime complexes, racemization of chiral group bonded to Co proceeds by X-ray irradiation without degradation of crystallinity. Racemization of methoxycarbonylethyl (mce) group has been examined for five cobaloxime complexes with different base as the second axial ligand, three of which did not give any indication of the reaction. Their crystal structures well explain the inactivity. Every stage of the change in the reactive crystals (base 4-chloropyridine, I; pyridine, II) has been revealed by X-ray analysis. In I, the mce groups suffer configurational and conformational changes at high temperature cooperatively. In II, rapid desolvation at room temperature is accompanied by conformational change of mce, and at 343 K random inversion occurs.
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