Synthetic strategies have been developed for the synthesis complexes of the types {[Re2Cl3(mu-dppm)(2)(CO)(2)](2)[mu-Y]}(+), where dppm = Ph2PCH2PPh2 and Y = [N(CN)(2)] or [C(CN)(3)], and [Re2Cl3(mu-PP)(CO)(L)](2)[mu-Ni(CN)(4)] (see structure), where PP = dppm or Ph2PC(=CH2)PPh2 (dppE) and L = CO or XyINC. The pairs of edge-sharing bioctahedral dirhenium(II) units are linked by single [N(CN)(2)](-), [C(CN)(3)](-), or [Ni(CN)(4)](2-) units which allow for electronic communication between the dimetal centers as shown by CV and DPV electrochemical studies.