Group 13 Ligand Supported Heavy‐Metal Complexes: First Structural Evidence for Gallium–Lead and Gallium–Mercury Bonds

Heavy‐metal complexes of lead and mercury stabilized by Group 13 ligands were derived from the oxidative addition of Ga(ddp) (ddp=HC(CMeNC 6 H 3 ‐2,6‐ i Pr 2 ) 2 , 2‐diisopropylphenylamino‐4‐diisopropyl phenylimino‐2‐pentene) with corresponding metal precursors. The reaction of Me 3 PbCl and Ga(ddp) afforded compound [{(ddp)Ga(Cl)}PbMe 3 ] ( 1 ) composed of GaPb IV bonds. In addition, the monomeric plumbylene‐type compound [{(ddp)Ga(OSO 2 CF 3 )} 2 Pb(thf)] ( 2 a ) with an unsupported Ga‐Pb II ‐Ga linkage was obtained by the reaction of [Pb(OSO 2 CF 3 ) 3 ] with Ga(ddp) (2 equiv). Compound 2 a falls under the rare example of a discrete plumbylene‐type compound supported by a nonclassical ligand. Interesting structural changes were observed when [Pb(OSO 2 CF 3 ) 3 ] ⋅ 2 H 2 O was treated with Ga(ddp) in a 1:2 ratio to yield [{(ddp)Ga(μ‐OSO 2 CF 3 )} 2 (OH 2 )Pb] ( 2 b ) at below −10 °C. Compound 2 b consists of a bent Ga‐Pb‐Ga backbone with a bridging triflate group between the GaPb bond and a weakly interacting water molecule at the gallium center. Similarly, the reaction of mercury thiolate Hg(SC 6 F 5 ) with Ga(ddp) (2 equiv) produced the bimetallic homoleptic compounds anti‐ [{(ddp)Ga(SC 6 F 5 )} 2 Hg] ( 3 a ) and gauche ‐[{(ddp)Ga(SC 6 F 5 )} 2 Hg] ( 3 b ), respectively, with a linear Ga‐Hg‐Ga linkage. Compounds 1 – 3 were structurally characterized and these are the first examples of compounds comprised of GaPb II , GaPb IV , and GaHg bonds.