Heavy-metal complexes of lead and mercury stabilized by Group 13 ligands were derived from the oxidative addition of Ga(ddp) (ddp = HC(CMeNC 6H32,6-iPr2)2, 2-diisopropylphenylamino-4- diisopropyl phenylimino-2-pentene) with corresponding metal precursors. The reaction of Me3PbCl and Ga(ddp) afforded compound' [{(ddp)Ga(Cl)}PbMe3] (1) composed of Ga-PbIv bonds. In addition, the monomeric plumbylene-type compound [{(ddp)Ga(OSO 2CF3)}:Pb(thf)] (2a) with an unsupported GaPb II-Ga linkage was obtained by the re-action of [Pb(OSO 2CF3)3] with Ga(ddp) (2 equiv). Compound 2a falls under the rare example of a discrete plumbylene-type compound supported by a nonclassical ligand. Interesting structural changes were observed when [Pb(OSO2CF3)3]·2H2O was treated with Ga(ddp) in a 1:2 ratio to yield [{(ddp)Ga(μ-OSO 2CF3)}2(OH2)Pb] (2b) at below -10°C. Compound 2b consists of a bent Ga-Pb-Ga backbone with a bridging triflate group between the Ga-Pb bond and a weakly interacting water molecule at the gallium center. Similarly, the reaction of mercury thiolate Hg(SC 6F5) with Ga(ddp) (2 equiv) produced the bimetallic homoleptic compounds anti-[{(ddp)Ga(SC6F5)}2Hg] (3a) and gauche[{(ddp)Ga(SC6F5)}2Hg] (3b), respectively, with a linear Ga-Hg-Ga linkage. Compounds 1-3 were structurally characterized and these are the first examples of compounds comprised of GaPbII, Ga-PbIv, and Ga-Hg bonds. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.