Divalent N I Compounds: Identifying new Carbocyclic Carbenes to Design Nitreones using Quantum Chemical Methods

Abstract

Nitreones are compounds with oxidation state 1 at the nitrogen, these compounds carry formal positive charge as well as two lone pairs of electrons at nitrogen center. These compounds are also known as divalent NI compounds and can be represented with the general formula L → N+ ← L, where L is an electron donating ligand. In the recent past, several divalent NI compounds have been reported with L = N‐heterocyclic carbene (NHC), remote N‐heterocyclic carbene (rNHC), carbocyclic carbene (CCC) and diaminocarbene. Recently, our group reported that a novel six‐membered CCC (cyclohexa‐2,5‐diene‐4‐[diaminomethynyl]‐1‐ylidene) can stabilize N+ center in nitreones. As an independent carbene, this species is very unstable. In this work, modulation of this CCC using (a) annulation, (b) heterocyclic ring modification, (c) substitutions adjacent to the carbenic carbon, (d) exocyclic double bond insertion and (e) ring contraction, has been reported. These modulations and quantum chemical analyses helped in the identification of five new six‐membered CCCs which carry improved donation and stability properties. Further, these CCCs were employed in the design of new divalent NI compounds (nitreones) which carry coordination bonds between ligands and N+ center. The molecular and electronic structure properties, and the donor→acceptor coordination interactions present in the resultant low oxidation state divalent NI compounds have been explored.