Reactive Dimerization of an N-Heterocyclic Plumbylene: C-H Activation with PbII.
Robin GuthardtJan OetzelJulia I SchweizerClemens BruhnRobert LangerMartin MaurerJan VíchaPavletta ShestakovaMax C HolthausenUlrich SiemelingPublished in: Angewandte Chemie (International ed. in English) (2019)
The N-heterocyclic plumbylene [Fe{(η5 -C5 H4 )NSiMe3 }2 Pb:] is in equilibrium with an unprecedented dimer in solution, whose formation involves the cleavage of a strong C-H bond and concomitant formation of a Pb-C and an N-H bond. According to a mechanistic DFT assessment, dimer formation does not involve direct PbII insertion into a cyclopentadienyl C-H bond, but is best described as an electrophilic substitution. The bulkier plumbylene [Fe{(η5 -C5 H4 )NSitBuMe2 }2 Pb:] shows no dimerization, but compensates its electrophilicity by the formation of an intramolecular Fe-Pb bond.