- OXIDATION-REDUCTION MECHANISMS - INNER-SPHERE AND OUTER-SPHERE ELECTRON TRANSFER IN THE REDUCTION OF IRON(III), RUTHENIUM(III), AND OSMIUM(III) COMPLEXES BY ALKYL RADICALS. MECHANISMS -
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Alkyl radicals are readily oxidized by the tris(phenanthroline) and tris(bipyridine) complexes ML//3**3** plus of iron(III), ruthenium(III), and osmium(III) in acetonitrile solution, the second-order rate constants easily exceeding 10**6 M** minus **1s** minus **1 at 25 degree C. Two oxidative processes are identified as (a) ligand substitution on the coordinated 1,10-phenanthroline to yield various alkylphenanthrolines and (b) cation formation to afford alkenes and N-alkylacetamides (after hydrolysis). Cation formation is characterized by extensive skeletal rearrangement of neopentyl, isobutyl, and n-propyl groups, whereas ligand substitution by the same alkyl radicals occurs without any rearrangement.
- Rollick,Kochi
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p. 1319 - 1330
(2007/10/02)
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