The Re-Cl-t bond that is cis to the mu-CO unit in the edge-sharing bioctahedral complex Re-2(mu-Cl)(mu-Co)(mu-dppE)(2)Cl-3(CO) (1b; dppE = Ph2PC(=CH2)PPh2 ) is labile toward substitution by anionic and neutral thiocyanate and cyanide containing metal fragments to afford mixed-metal Re2Pd2, Re2W, and Re2Pt assemblies. These products (3-5) retain the Re=Re bond of the parent dirhenium(II) complex as demonstrated by the crystal structure of the Re4Pd2 cluster [Re2(mu-Cl)(mu-CO)(mu-dPPE)(2)Cl-2(Co)](2)(mu-NCs)(2)[Pd-2(mu-SCN)(mu-NCS)Cl-2]. [GRAPHICS] /INF>]. [GRAPHICS]