Reactive Dimerization of an N‐Heterocyclic Plumbylene: C−H Activation with PbII

The N‐heterocyclic plumbylene Fe{(η⁵‐C₅H₄)NSiMe₃}₂Pb:] 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 Pb^II insertion into a cyclopentadienyl C?H bond, but is best described as an electrophilic substitution. The bulkier plumbylene Fe{(η⁵‐C₅H₄)NSitBuMe₂}₂Pb:] shows no dimerization, but compensates its electrophilicity by the formation of an intramolecular Fe?Pb bond.