Reaching for two new stable ambiphilic quinoline‐derived N ‐heterocyclic carbenes at DFT level

A detailed investigation on the thermodynamic and kinetic stability of four carbenic tautomers of quinoline 1 , including quinoline‐2‐ylidene 2 , quinoline‐3‐ylidene 3 , quinoline‐4‐ylidene 4 , and 3,4‐dihydroquinoline‐4‐ylidene 5 , reveals that singlet planar six‐membered ring N‐heterocyclic carbenes (NHCs) 2 and 4 have less stability than Arduengo type NHC but seems to have enough conceivably for reaching at B3LYP/aug‐cc‐pVTZ//B3LYP/6–31+G* and B3LYP/6–311++G**//B3LYP/6–31+G* levels. All these six‐membered NHCs are extremely ambiphilic with the more nucleophilic and electrophilic characters compared to the Arduengo type one. The aromaticity of singlet 2 and 4 is a significant contributor to their stability which is confirmed through their Nucleus‐independent chemical shift(1) zz values. Finally, among 2–5 , the normal NHC 2 is thermodynamically preferred but the remote NHC 4 is kinetically proffered over the other isomeric carbenes. The effects of different N‐ or C‐substituted NHCs of 2 are studied using appropriate isodesmic reactions. The trimethylsilyl substituent exhibits slightly larger carbene stabilization in quinoline‐derived NHCs than the pyridine analogue. © 2014 Wiley Periodicals, Inc.