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NMR study of complexation in the catalyst - hydroperoxide, catalyst - alcohol, and catalyst - olefin - hydroperoxide systems

Journal Article · · Kinet. Catal. (Engl. Transl.); (United States)
OSTI ID:5950669
On the basis of paramagnetic shifts and the broadening of NMR lines of hydroperoxide protons of cyclohexyl- and 1-methylcyclohexyl peroxides in haptane solution containing Mo(O) hexacarbonyl or Co(II) acetylacetonate, the authors have determined the heats of complexation and the lifetimes of hydroperoxide ligands in the metal - complex-former coordination sphere, and the activation energies of their emergence from the coordination sphere. They have determined the distances from the complex former of the central metal to the hydroxyl protons of the ligand (hydroperoxide, alcohol), and the hyperfine electron - nucleus interaction constants for the ligand hydroxyl protons in the complex. Molybdenum hexacarbonyl forms labile outer-sphere complexes with hydroperoxides and alcohols. However Co(II) acetylacetonate forms complexes that are stronger and intermediate between inner-sphere and outer-sphere complexes.
Research Organization:
Lensovet Leningrad Technological Institute (USSR)
OSTI ID:
5950669
Journal Information:
Kinet. Catal. (Engl. Transl.); (United States), Journal Name: Kinet. Catal. (Engl. Transl.); (United States) Vol. 29:4; ISSN KICAA
Country of Publication:
United States
Language:
English