Coupling of edge-sharing bioctahedral dirhenium(II) units through the agency of [N(CN)(2)](-), [C(CN)(3)](-), and [Ni(CN)(4)](2-) linkages.

Synthetic strategies have been developed for the synthesis of complexes of the types {[Re2Cl3(μ-dppm)2(CO)2]2[μ-Y]}+, where dppm = Ph2PCH2PPh2 and Y = [N(CN)2] or [C(CN)3], and [Re2Cl3(μ-PP)(CO)(L)]2[μ-Ni(CN)4] (see structure), where PP = dppm or Ph2PC(CH2)PPh2 (dppE) and L = CO or XylNC. 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.