Electron transfer to complex ligands. Radical anions and organomagnesium radical complexes of 2,2'-bipyridines and 1,10-phenanthrolines

Journal of the American Chemical Society, 104 (14): 3833--3837 (1982)
DOI: 10.1021/ja00378a010


The bidentate complex ligands 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine 1,10-phenanthroline, and 4,7-dimethyl-1,10-phenanthroline were reduced to radical anions by K metal and to organomagnesium radical complexes in a single electron transfer reaction of Ph2Mg. Well resolved ESR were analyzed on the basis of HMO calcns. In the case of the 1,10-phenanthrolines there are 2 LUMOs available to accommodate the addnl. electron; a comparison of the spin distributions demonstrates that, in contrast to earlier assumptions, it is the 5b1 orbital that is singly occupied. This result explains the similar properties of corresponding 2,2'-bipyridine and 1,10-phenanthroline metal complexes. on SciFinder(R)



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