Reduction of a 1,4-diazabutadiene and 2,2’-bipyridine using magnesium(I) compounds

Abstract

Abstractβ-diketiminate coordinated magnesium(I) compounds, [{(ArNacnac)Mg}2] (ArNacnac = [(ArNCMe)2CH]– (Ar = 2,6-diisopropylphenyl (Dip) or mesityl (Mes)), have been utilized as reducing agents in reactions with the redox active 1,4-diazabutadiene, (ButNCH)2 (ButDAB), and 2,2’-bipyrine (bipy). These reactions led to one-electron reductions of the unsaturated substrate, and formation of the highly colored radical complexes, [(ArNacnac) Mg(ButDAB•)] and [(MesNacnac)Mg(bipy•)(bipy)]. The X-ray crystal structures of the compounds reveal each to possess one singly reduced ButDAB or bipy ligand.

Ketyl Radicals Generated from Magnesium(I) Compounds: Useful Reagents for C−C Bond Forming Reactions

“…[24] The mechanism of these reactions presumably involves an intermediate, 12, in which both the ketyl and phenanthroline units are coordinated to the ( Mes Nacnac)Mg fragment. [28] This then allows a regioselective nucleophilic attack of the ketyl carbon at an ortho-carbon center of phenanthroline, subsequently leading to elimination of hydrogen, to give the observed products. With that said, the elimination of H 2 gas was not observed during the course of the reaction.…”