In tetrahydrofuran solution redox condensation reactions between the salts NEt4[Re2(mu-PR2)(CO)8] (R = Ph, Cy) and ClM(CO)(PPh3)2 (M = Rh, Ir) in the presence of the chloride scavenger TIPF6 and CO(g) at 20-degrees-C in 3 h gave four red compounds of the type Re2(mu-PR2)(CO)8[M(CO)2PPh3] (M = Rh, R = Ph (1) and Cy (2); M = Ir, R = Ph (3), and Cy (4)) which were separated. The remaining two red title compounds ReRh(mu-CO)2(mu-PR2)(CO)2(PPh3)2[Re(CO)4] (R = Ph (5), Cy (6)) were obtained from the reaction of [Rh(COD)(PPh3)2]BF4 and the aforementioned dirhenium salts in thf solution under reflux conditions within 20 h. 1-4 were characterized by P-31 NMR, upsilon(CO) IR, and UV/vis spectroscopic data. The molecular structures of the saturated triangular cluster complexes 1 and 4 and that of unifold unsaturated 6 were identified by single-crystal X-ray data. Compounds 1, 4, and 6 crystallize in the monoclinic space groups P2(1)/n (Z = 4), P2(1)/c (Z = 8), and P2(1)/n (Z = 4). For 1, a = 12.138(2) angstrom, b = 23.376(4) angstrom, c = 14.019(3) angstrom, and beta = 90.65(2)-degrees; for 4, a = 12.694(3) angstrom, b = 20.700(3) angstrom, c = 32.769(6) angstrom, and beta = 101.06(1)-degrees; and for 6, a = 12.757(3) angstrom, b = 32.106(7) angstrom, c = 13.999(3) angstrom, and beta = 94.04(2)-degrees, respectively. The (mu-P)Re2M core in 1 and 4 is planar. These bridged Re atoms have octahedrally distorted ligand environments, while the M atoms are coordinated pseudotrigonal bipyramidally by two axial CO groups, an equatorial PPh3, and two equatorial Re atoms. The values of the sigma(Re-Re) and average sigma(Re-M) bond lengths are 3.169(1) and 2.988(1) angstrom in 1 and 3.133(1) and 2.962(1) angstrom in 4.