Metallocomplexes, exhibiting catecholate binding mode for o-quinone, annulated with dithiete cycle

Novel catecholate complexes (ditCat)SbPh3 (1), (ditCat)Ni(2,2 '-bpy) (2) and (3,6-tBu-ditCat)VCp2 (3), containing annulated dithiete cycle, were synthesized by reactions of bifunctional o-quinone, annulated with dithiete ring (ditQ) with SbPh3, (2,2 '-bpy)Ni(CO)2 and VCp2, respectively. The structures of complexes 1 and 2 were confirmed by X-ray analysis. X-band EPR spectrum of complex 3 in THF has typical of d1-complexes of vanadium (IV) 8-lined pattern. Complex 1 in toluene reversibly binds molecular dioxygen with formation of spiroendoperoxide (3,6-tBu-ditCat)SbPh3.O2.C7H8 (4).

Automated summary

Novel catecholate complexes (ditCat)SbPh3 (1), (ditCat)Ni(2,2 '-bpy) (2) and (3,6-tBu-ditCat)VCp2 (3) were synthesized by reactions of bifunctional o-quinone with dithiete ring annulated compounds. Complexes 1 and 2 structures were confirmed by X-ray analysis, while complex 3 showed typical d1-complexes of vanadium (IV) in its X-band EPR spectrum. Complex 1 can reversibly bind dioxygen to form a spiroendoperoxide in toluene.