On the Formation of “Free Radicals” from Alkylcobalt Complexes

Abstract

The photolysis of alkylcobaloximes such as 1 affords free radicals. This was deduced from reactivity and selectivity studies in which the intermediates generated from cobaloximes as well as via vitamin B12 behaved precisely as those from other radical sources. This finding is very important for the planning of syntheses and has implications for the discussions of vitamin B12-catalyzed reactions in living organisms. Hitherto, the general opinion was that radicals so generated are somewhat stronger bound to the cobalt complex (dmgH2 = 2,3-butanedionedioxime, py = pyridine).