A tetranuclear cluster containing two quadruply bonded cis-Mo-2(DAniF)2 units (DAniF = N,N-di-p-anisylformamidinate) linked by four hydroxide groups (1) was obtained by hydrolysis Of [Mo-2(cis-DAniF)(2)](mu-OCH3)(4). Analogous compounds linked by two bidentate bridges (o-O2C6H4 for 2, o-O2C10H6 for 3, and o-S2C6H4 for 4) were synthesized by direct assembly of the corner species precursor [M,02(cis-DAniF)2(NCCH3)(4)](BF4)(2) and the respective protonated ligands. All four compounds were characterized by X-ray crystallography. Cyclic voltammograms of the 0-linked compound 2 and the S analogue.4 show two reversible one-electron-oxidation processes with potential separations (triangle E-1/2) of 474 and 776 mV, respectively. The large increase of about 300 mV in triangle E-1/2 for the S analogue relative to that of the 0 compound is consistent with a large increase in electronic communication. This enhancement occurs despite the increase of ca. 0.45 A in nonbonding separation between the midpoints of the Mo-2 units, which changes from 3.266 A in 2 to 3.72 A in 4, and the increase of ca. 0.4 A in WE distances as E changes from 0 to S. Density functional theory calculations show that the increase in electronic communication between the metal centers in 4 is due to a superexchange pathway involving d and p orbitals in the linker E atoms that is less important in 2.