Sodium borohydride reduction of cobaloxime complexes. An electron-transfer, free-radical process

Abstract

In 1969 Coliman and co-workers1 reported that allenylcobaloxime complexes undergo reductive removal of the allenyl group on treatment with sodium borohydride. The reduction of 1 (R = H) produced only aliene, while the reduction of 1

Synthesis of Cobaloxime-Substituted α,β-Unsaturated Acyl Complexes via Reactions of Cobaloxime Anions and/or Hydrides with Ynones, Ynoates, and α,β-Unsaturated Acyl Electrophiles

“…In this traditional method of cobaloxime anion generation, ynone or ynoate was quickly added, followed shortly thereafter (ca. 5 min) by acetic acid , entries 6−10), this method produced the alkene isomer where cobaloxime and the α alkene proton were anti .…”

Alkylcobalt(III) compounds with ammine ligands

“…The bond homolysis is in most cases achieved by photolysis [2] although other methods like reduction [3], oxidation [4], thermolysis [5,6], or sonolysis [7,8] have also been employed. Central to our own work is the recent finding that the pentaamminemethylcobalt(III) cation acts as a radical methylation agent towards the C8 carbon atom of guanosine 5 0 -monophosphate and adenosine 5 0 -monophosphate in aqueous solution at near neutral pH [9].…”