η3‑Allyl Coordination at Pb(II)

Allylmagnesium chloride and methyl-propenyl-magnesium bromide were reacted with bulky substituted organolead and organotin halides (Ar*PbBr)2, (Ar′PbBr)2, (Ar*SnCl)2 (Ar* = 2,6-trip2C6H3-, trip = 2,4,6-triisopropylphenyl, Ar′ = 2,6-mes2C6H3-, mes = 2,4,6-trimethylphenyl). The allyl ligand coordinates in an η3-coordination mode at organoplumbylene fragments. In the solid state as well as in solution, η3-coordination was characterized by crystal structure analysis and Saunders’ isotopic perturbation technique. For the plumbylene Ar*Pb­(C3H5), a solid state 207Pb magic angle spinning (MAS) NMR spectrum could be obtained. The isotropic chemical shift is −435 ppm, and the magnitude of the 207Pb chemical shift tensor of 7000­(500) ppm is among the greatest observed experimentally. The methylallyl ligand coordinated at a plumbylene fragment exhibits two short and one long Pb–C interaction. In reaction with aniline, the allyl ligand reacts as a leaving group to give amidoplumbylenes.