The lability of the terminal Re-CI bond that is cis to the bridging CO ligand in the edge-sharing bioctahedral complexes Re-2(mu -Cl)(mu -CO)(mu -PP)(2)Cl-3(L), where PP = Ph2PC(=CH2)PPh2 (dppE) when L = CO (1) and PP = Ph2PCH2PPh2 (dppm) when L = CO (2) or XyINC (3), has been exploited in the preparation of mixed-metal Re4Pd2, Re2Ag, Re2W, Re2Pt, and Re2Rh assemblies, in which the dirhenium units are bound to the other metals through NCS or CN bridges. These complexes, which retain the Re=Re bonds of the parent dirhenium complexes, comprise the novel centrosymmetric complex [Re2Cl3(mu -dppE)(2)(CO)(2)(mu -NCS)](2)Pd-2(mu -SCN)(mu -NCS)Cl-2 (9), and the trimetallic complexes Re2CI3(mu -dppE)(2)(CO)(2)[(mu -NC)Ag(CN)] (10), Re2Cl3(mu -dppE)(2)(CO)(2)[(u-NC)W(CO)(5)] (11), [Re2Cl3(mu -dppE)(2)(CO)(2){(u-NC)Pt(CN)(CN-t-BU)(2)}]PF6 (12), [Re2Cl3(mu -dppE)(2)(CO)(2){(mu -N(CN)(2))Rh(CO)-(PPh3)(2)}]O3SCF3 (13), and Re2Cl3(mu -dppm)(2)(CO)(2)[(mu -NC)W(CO)(5)] (16). The identities of 9 and 16 have been established by X-ray crystallography, and all complexes characterized by IR and NMR spectroscopy and cyclic voltammetry. The reactions of the dicarbonyl complex 1, and the isomeric pair of complexes Re2Cl4(mu -dppm)(2)-(CO)(CNXyl), which have edge-sharing bioctahedral (ESBO) (3) and open bioctahedral (OBO) (4) geometries, with Na[N(CN)(2)] and K[C(CN)(3)] have been used to prepare complexes in which the uncoordinated CN groups have the potential to coordinate other mono- or dimetal units to form extended arrays. The complexes which have been prepared and characterized are the monosubstituted species Re2Cl3(X)(mu -dppE)(2)(CO)(2) (X = N(CN)(2) (14) or C(CN)(3) (15)) and Re2Cl3(X)(mu -dppm)(2)(CO)(CNXyl) (X = N(CN)(2) (17) or C(CN)(3) (18) with ESBO structures; X = N(CN)(2) (19) or C(CN)(3) (20) with OBO structures), of which 15, 18, and 20 have been characterized by single-crystal X-ray structure determinations. The substitutional labilities of the Re-Cl bonds in the complexes Re2C4(mu -dppm)(2)(CO) (5), Re2C4(mu -dppm)(2)(CNXyl) (6), and Re2Cl4(mu -dppm)(2) (7) toward Na[N(CN)(2)] and K[C(CN)(3)] have also been explored and the complexes Re2Cl3(X)(mu -dppm)(2)(CO) (X = N(CN)(2) (21) or C(CN)(3) (22)), Re2Cl3(X)(mu -dppm)(2)(CNXyl) (X = N(CN)(2) (23) or C(CN)(3) (24)), Re2Cl2(X)(2)(mu -dppm)(2)(CNXyl) (X = N(CN)(2) (25) or C(CN)(3) (26)), Re-2[N(CN)(2)](4)(mu -dppm)(2) (27), and Re-2[C(CN)(3)](4)(mu -dppm)(2) (28) isolated in good yield. Single-crystal X-ray structure determinations of 24, 26, and 27 have shown that the Re-Re triple bonds pre-sent in the starting materials 5-7 are retained in these products.