Heterobimetallic complexes of a vanadium(V) and rhenium(VII) combination connected by mu-oxido bridge [LVO(mu-O)ReO3]center dot H2O [H2L = N, N'-ethylene bis(salicylideneimine) (H(2)salen) and its methoxy derivative] (1, 2) are reported. The compounds have been prepared by a single-pot synthesis in which the precursor [(VOL)-O-IV] complexes are allowed to be oxidized aerially in the presence of added perrhenate. The oxidized [(VOL)-O-V](+) species accommodate the ReO4-anion in their vacant coordination site, trans to the terminal oxido group, providing the complexes 1 and 2. The later generates a binuclear oxovanadium(V) compound [H(2)en][(TBC)VO(mu-TBC)(2)OV(TBC)]center dot 5H(2)O (3) when treated with tetrabromocatechol. Single crystal X-ray diffraction analysis and H-1 NMR spectroscopy have been used to establish their identities. In compound 2, the Re(1)-O(11)-V(1) bridge angle is barely linear [170.2(3)degrees] with a Re...V separation of 3.9647(9) angstrom. The redox behavior of 1 and 2 are quite interesting, each undergoing two reductions both in the positive potential range at E-1/2 = 0.59 (process I) and E-1/2 = 0.16 V (process II) versus Ag/AgCl reference (corresponding potentials are 0.59 and 0.18 V for 2). Process I has a single-electron stoichiometry involving the [VO(salen)] part of the complexes as established by combined coulometry-Electron Paramagnetic Resonance (EPR) experiments which provide an eight-line isotropic EPR pattern at room temperature (< g > = 1.967; < A > = 87 x 10(-4) cm-1), characteristic of an unpaired electron being coupled to a vanadium nuclear spin (V-51, I = 7/2). The almost linear V-O-Re bridge in 1 and 2 allows this unpaired electron to interact effectively with the neighboring Re nuclear spin, leading to familiar "two-line pattern" superhyperfine coupling (A ((185),Re-187) = 20.7 x 10(-4) cm(-1)). Process II, on the other hand, is based on a Re(VII/VI) electron transfer as confirmed by differential pulse and normal pulse voltammetric experiments.