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Divalent N I Compounds: Identifying new Carbocyclic Carbenes to Design Nitreones using Quantum Chemical Methods
Author(s) -
Patel Neha,
Arfeen Minhajul,
Singh Tejender,
Bhagat Shweta,
Sakhare Ajay,
Bharatam Prasad V.
Publication year - 2020
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26417
Subject(s) - carbene , chemistry , divalent , lone pair , stereochemistry , ring (chemistry) , ligand (biochemistry) , oxidation state , double bond , crystallography , organic chemistry , molecule , metal , catalysis , biochemistry , receptor
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 N I 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 N I compounds have been reported with L = N ‐heterocyclic carbene (NHC), remote N ‐heterocyclic carbene ( r NHC), 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 N I 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 N I compounds have been explored.