DFT Prediction of Multitopic N‑Heterocyclic Carbenes Using Clar’s Aromatic Sextet Theory

Existence of several multitopic N-heterocyclic carbene (NHC) ligands with up to four carbene centers have been predicted on the basis of Clar’s aromatic sextet theory. Assessment on stability and reactivity of NHCs was made by quantifying aromaticity, aromatic stabilization energy (E_aroma), strength of carbene lone pair, proton affinity, and CuCl binding energy. On NICS(0) and HOMA scales of aromaticity, several NHCs showed high aromaticity, while E_aroma (17.2–19.4 kcal/mol) indicated substantial stability for the N-heterocycle. Homodesmotic reactions suggested that heat of formation of most of the newly designed carbenes is very close to that of the existing bis-NHCs. Designing a multitopic ligand through branching via C_sp3 linkage was very effective as it improved the stability of the carbene. Electrostatic potential minimum (V_min) at the carbene lone pair suggested that annelation of heterocycle to a benzenoid ring or branching through C_sp3 linkage can only marginally influence the electron donating power of the ligand. Hence, all multitopic NHCs showed proton affinity (252.3–267.4 kcal/mol) and CuCl binding energy (62.9–66.6 kcal/mol) very close to those of 1,3-dimethylimidazolidine-2-ylidene (1). It has also been demonstrated that branched multitopic 3-dimensional NHCs are attractive for designing metal–organic framework with narrow (1–1.5 nm) cage/pore size.