Abstract
Protonated forms of the molecules of ethylene derivatives with the general formula C2X2Y2 (X=Y=H) (1), F (2), CH3 (3) CH3 (4); X=F, Y=H:cis-(5)trans- (6)) were calculated by theab initio MP2/6-31 G* method with full geometry optimization. The minima and saddle points located on the potential energy surface (PES) of the protonated ethylene molecule correspond to the stationary states and transition states of proton migration, respectively. The stationary states are characterized by a nonclassical geometry of carbocations similar to that of π-complexes, whereas the transition states have a classical structure. Unlike1, the carbocations of molecules2–6 have the classical structure. The saddle points on the PES of the ethylene derivatives correspond to the structures of the π-complex type, which are the transition states of proton migration between the C atoms of the ethylene bond. The barrier to rotation about, the C−C bond depends essentially on the substituent nature.
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Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1333–1337, August, 2000.
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Borisov, Y.A. Anab initio quantum-chemical study of proton addition to F-, Ch3-, and CF3-substituted ethylene derivatives. Russ Chem Bull 49, 1327–1331 (2000). https://doi.org/10.1007/BF02495072
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DOI: https://doi.org/10.1007/BF02495072