The trichromium-lead complex [Pb{Cr(CO)(5)}(3)](2-)(1) was isolated from the reaction of PbCl2 and Cr(CO)(6) in a KOH/MeOH solution, and the new mixed chromium-iron-lead complex [Pb{Cr(CO)(5)}{Fe(CO)(4)}(2)](2-) (3) was synthesized from the reaction of PbCl2 and Cr(CO)(6) in a KOH/MeOH solution followed by the addition of Fe(CO)(5). X-ray crystallography showed that 3 consisted of a central Pb atom bound in a trigonal-planar environment to two Fe(CO)(4) and one Cr(CO)(5) fragments. When complex 1 reacted with 1.5 equiv of Mn(CO)(5)Br, the Cr(CO)(4)-bridged dimeric lead chromium carbonyl complex [Pb2Br2Cr4(CO)(18)](2-) (4) was produced. However, a similar reaction of 3 or the isostructural triiron-lead complex [Pb{Fe(CO)(4)}(3)](2-) (2) with Mn(CO)(5)Br in MeCN led to the formation of the Fe3Pb2-based trigonal-bipyramidal complexes [Fe-3(CO)(9){PbCr(CO)(5)}(2)](2-) (6) and [Fe-3(CO)(9){PbFe(CO)(4)}(2)](2-) (5), respectively. On the other hand, the Ru3Pb2-based trigonal-bipyramidal complex [Ru-3(CO)(9){PbCr(CO)(5)}(2)](2-) (7) was obtained directly from the reaction of PbCl2, Cr(CO)(6), and Ru-3(CO)(12) in a KOH/MeOH solution. X-ray crystallography showed that 5 and 6 each had an Fe3Pb2 trigonal-bipyramidal core geometry, with three Fe(CO)(3) groups occupying the equatorial positions and two PbFe(CO)(4) or PbCr(CO)(5) units in the axial positions, while 7 displayed a Ru3Pb2 trigonal-bipyramidal geometry with three equatorial Ru(CO)(3) groups and two axial PbCr(CO)(5) units. The complexes 3-7 were characterized spectroscopically, and their nature, formation, and electrochemistry were further examined by molecular orbital calculations at the B3LYP level of density functional theory.