Following our quest for stable group 14 divalents, novel N-heterocyclic plumbylenes (NHPbs), composed of 2,4,6-cycloheptatriene-2,7-diazaplumbylene (1), benzannulated with one (2), two (3, 4), and three benzene rings (5), are compared and contrasted at the density functional theory level. Results indicate that in going from 1 to 5, the absolute values of singlet-triplet energy gap (ΔEs-t) and band gap (ΔEH-L) increase, while nucleophilicity (N), electrophilicity (ω), and chemical potential (μ) decrease. The most benzannulated structure, ([a,c,e]tribenzo)cyclohepta-2,7-diazaplumbylene (5), turns out as the most stable plumbylene for showing the most negative ΔEs-t of − 194.94 kcal/mol. Furthermore, 5 shows the highest ΔEH-L (− 2.75 eV), with the lowest N (1.31 eV), ω (8.20 eV), μ (− 7.15 eV), and charge of (+ 0.736) on Pb atom. Isodesmic reactions of 1-5 with common transition metal halides, MX2, give forty new metal complexes of 1M-X-5M-X, where M = Pt and Pd, while X = F, Cl, Br, and I. Their complexation energies (ΔECom) indicate that 1-5 are rather stronger ligands with Pt than Pd. Bader’s atoms in molecules (AIM) and NBO analyses show the partial covalent and partial electrostatic nature of Pb-M bonds.