Complexation of the ambidentate ligand 4-mercaptobenzoate (4-SH-C6H4CO2H, H(2)mba) by the macrocyclic complex [Ni2L(mu-Cl)]ClO4 (L-2 represents a 24-membered macrocyclic hexaazadithiophenolate ligand) has been examined. The monodeprotonated Hmba ligand reacts with the Ni-2 complex in a selective manner by substitution of the bridging chlorido ligand to produce mu(1,3)-carboxylato-bridged complex [Ni2L(Hmba)](+) (2(+)), which can be isolated as an air-sensitive perchlorate (2ClO(4)) or tetraphenylborate (2BPh(4)) salt. The reactivity of the new mercaptobenzoate complex is reminiscent of that of a free thiophenolate ligand. In the presence of air, 2ClO(4) dimerizes via a disulfide bond to generate tetranuclear complex [{Ni2L}(2)(O(2)CC(6)H4(S))(2)](2+) (3(2+)). The auration of 2ClO(4) with [AuCl(PPh3)], on the other hand, leads to monoaurated complex [(Ni2L)-L-II(mba)(AuPPh3)-P-I](+) (4(+)). The bridging thiolate functions of the N6S2 macrocycle are deeply buried and are unaffected/unreactive under these conditions. The complexes were fully characterized by electrospray ionization mass spectrometry, IR and UV/vis spectroscopy, density functional theory, cyclic voltammetry, and X-ray crystallography [for 3(BPh4)(2) and 4BPh(4)]. Temperature-dependent magnetization and susceptibility measurements reveal an S = 2 ground state that is attained by ferromagnetic coupling between the spins of the Ni-II ions in 2ClO(4) (J = +22.3 cm(1)) and 4BPh(4) (J = +20.8 cm(1); H = -2JS(1)S(2)). Preliminary contact-angle and X-ray photoelectron spectroscopy measurements indicate that 2ClO(4) interacts with gold surfaces.