Graphical Abstract: The steric protection offered by the macrobinucleating hexaazaditiophenolate 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 helical μ4-hexa- sulfide 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.