•A magnesium complex bearing radical bipyridyl was prepared.•The complex can act as a Mg(I) synthon in activation of small molecules.•To further illustrate the reaction mechanism, the DFT calculations were used.The reduction of [HC(C(Me)N-2,6-iPr2C6H3)2]MgBr (1) with potassium graphite in the presence of 2,2’-bipyridine (bipy) gives a reduced 2,2’-bipyridyl magnesium complex [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(bipy) (2) in good yield. Complex 2 is a useful electron transfer reagent as demonstrated by its reactivity with azobenzene, diphenyl disulphide, diphenyl diselenide and Ph2CS, yielding the azobenzenyl radical magnesium complex [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(PhNNPh)(THF) (3), magnesium thiolate [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(SPh)(bipy) (4), magnesium selenolate [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(SePh)(bipy) (5), and radical substitution compound [HC(C(Me)N-2,6-iPr2C6H3)2]Mg[(bipy)(SCPh2)] (6), in good yields. Moreover, the density functional theory (DFT) studies have been undertaken to rationalize the forming process of compound 6.Download high-res image (158KB)Download full-size image