The reaction of Ph(2)BiCl with the dinuclear group VI anions [M(2)(CO)(10)](2-) (M = Cr, Mo, W) produces the isostructrual mixed organo-metal complexes [Ph(2)Bi{M(CO)(5)}(2)](-) ([1a](-), M = Cr; [1b](-), M = Mo; [1c](-), M = W). The [PPN](+) salts of these three clusters were characterized both spectroscopically and structurally. [PPN]-[1a] crystallizes in the triclinic space group P $($) over bar$$ 1 (No. 2) with cell constants a = 12.622(6) Angstrom, b = 12.800(6) Angstrom, c = 16.798(6) Angstrom, alpha = 84.05(3)degrees, beta = 87.89(3)degrees, gamma = 88.86(3)degrees, and V = 2697.3(3.7) Angstrom(3), [PPN][1b] crystallizes in an isomorphous unit cell with a = 12.738(4) Angstrom, b = 12.967(3) Angstrom, c = 16.817(7) Angstrom, alpha = 84.60(3)degrees, beta = 87.95(3)degrees, gamma = 88.38(3)degrees, and V = 2762.9(3.0) Angstrom(3). [PPN][1c] crystallizes as a combination toluene/ether solvate in the monoclinic space group P2(1)/n (No. 14) with unit cell constants a = 9.833(5) Angstrom, b = 28.166(10) Angstrom, c = 24.037(14) Angstrom, beta = 94.79(5)degrees, and V = 6634.3(5.7) Angstrom(3). The analogous reaction of Ph(2)BiCl with [Fe-2(CO)(8)](2-) yields [Ph(2)Bi{Fe(CO)(4)}(2)](-) ([2](-)). This complex can also be prepared from the reaction of the previously reported [Ph(2)BiFe(CO)(4)](-) with Fe-2(CO)(9). Similarly, the reaction of [Ph(2)BiFe(CO)(4)](-) with Cr(CO)(5)THF generates the heterometallic cluster [Ph(2)Bi{Fe(CO)(4)}{Cr(CO)(5)}](-) ([3](-)). [Et(4)N][2] crystallizes in the monoclinic space group P2(1)/n (No. 14) with cell constants a = 13.064(3) Angstrom, b = 14.309(3) Angstrom, c = 16.951(3) Angstrom, beta = 100.21(3)degrees, and V = 3118.5(1.1) Angstrom(3). [PPN][3] crystallizes as an ether solvate in the space group P $($) over bar$$ 1 (No. 2) with cell constants a = 10.998(2) Angstrom, b = 16.244(3) Angstrom, c = 17.203(3) Angstrom, alpha = 85.60(3)degrees, beta = 76.42(3)degrees, gamma = 80.13(3)degrees, and V = 2941.1(9) Angstrom(3). Comparison of the structural parameters in these and other related complexes indicates that the hybridization of the bismuth atom is dependent on its coordination environment. Initial attempts at producing higher nuclearity clusters through controlled oxidations have led to complete degradation of the complexes and production of simple metal carbonyl compounds such as Cr(CO)(5)(MeCN). In this case, the identity of the carbonyl compound was confirmed crystallographically. Cr(CO)(5)(MeCN) crystallizes in the space group P $($) over bar$$ 1 (No. 2) with unit cell constants a = 6.2140(10) Angstrom, b = 12.167(2) Angstrom, c = 13.402(3) Angstrom, alpha = 85.38(3)degrees, beta = 86.84(3)degrees, gamma = 86.30(3)degrees, V = 1006.6(3) Angstrom(3), and Z = 4.