The Heaviest Bottleable Metallylone: Synthesis of a Monatomic, Zero-Valent Lead Complex ("Plumbylone").

The elusive plumbylone {[SiII (Xant)SiII ]Pb0 } 3 stabilized by the bis(silylene)xanthene chelating ligand 1, [SiII (Xant)SiII =PhC(NtBu)2 Si(Xant)Si(NtBu)2 CPh], and its isolable carbonyl iron complex {[SiII (Xant)SiII ]Pb0 Fe(CO)4 } 4 are reported. The compounds 3 and 4 were obtained stepwise via reduction of the lead(II) dibromide complex {[SiII (Xant)SiII ]PbBr2 } 2, prepared from the bis(silylene)xanthene 1 and PbBr2 , employing potassium naphthalenide and K2 Fe(CO)4 , respectively. While the genuine plumbylone 3 is rather labile even at -60 °C, its Pb0 →Fe(CO)4 complex 4 turned out to be relatively stable and bottleable. However, solutions of 4 decompose readily to elemental Pb and {[SiII (Xant)SiII ]Fe(CO)3 } 5 at 80 °C. Reaction of 4 with [Rh(CO)2 Cl]2 leads to the formation of the unusual dimeric [(OC)2 RhPb(Cl)Fe(CO)4 ] complex 6 with trimetallic Rh-Pb-Fe bonds. The molecular and electronic structures of 3 and 4 were established by Density Functional Theory (DFT) calculations.