The steric protection offered by the macrobinucleating hexaaza-di tiophenolate ligand (L) allows for the preparation of the first stable dinuclear nickel(II) borohydride bridged complex, which reacts rapidly with elemental sulphur producing a tetranuclear nickel(II) complex [{(L)Ni2}2(μ-S6)]2 bearing a helicalμ4-hexasulfi de ligand. The [(L)CoII2]2 fragment have been able to trap a monomethyl orthomolybdate in the binding pocket. Unusual coordination modes of substrate in dinuclear macrocyclic compounds was demonstrated.