Kinetically stable high-energy isomers of C14H12 and C12H10N2 derived from cis-stilbene and cis-azobenzene.
Following on from our recent enforced geometry optimization (EGO) investigation of isomerization in cis-stilbene (J Comput Chem, in press) we report the discovery of two interesting new, symmetrical "fused sandwich" isomers of both cis-stilbene and the related cis-azobenzene. The isomers were obtained by applying external forces to pairs of carbon atoms from each of the benzene rings in cis-stilbene and cis-azobenzene simultaneously, and are all at least 100 kcal mol(-1) higher in energy than the starting material. Each new structure was characterized as a minimum by vibrational analysis. Despite their high energy, all of the new isomers appear to be kinetically stable with respect to rearrangement back to cis-stilbene or cis-azobenzene, respectively.
Baker
Jon
J
Parallel Quantum Solutions, 2013 Green Acres Road, Fayetteville, AR 72703, USA. baker@pqs-chem.com
Wolinski
Krzysztof
K
D001391:Azo Compounds / Q000737:chemistry*; D003198:Computer Simulation; D007536:Isomerism; D008958:Models, Molecular; D015394:Molecular Structure; D013059:Spectrum Analysis, Raman; D013267:Stilbenes / Q000737:chemistry*; D013816:Thermodynamics
D001391:Azo Compounds; D013267:Stilbenes; C009850:azobenzene