title: Quantum chemical study of solvent and substituent effects on the 1,5-hydride shift in 2,6-dimethyl-2-heptyl cations.
abstract: The mechanism of the degenerate 1,5-hydride shift in 2,6-dimethyl-2-heptyl cations has been investigated using ab initio MP2 and density functional theory (DFT) hybrid (B3LYP) calculations. The potential-energy profile for the 1,5-hydride shift consists of three minima corresponding to two equivalent acyclic carbocations and one symmetrically mu-hydrido-bridged carbocation, while two equivalent unsymmetrically hydrido-bridged carbocations were located as transition-state structures. The calculated relative energy differences between acyclic carbocations and symmetrically mu-hydrido-bridged structure are significantly affected by introduction of alkyl and (CH2)n-substituents at the C4 position of the 2,6-dimethyl-2-heptyl cation structure. DFT self-consistent isodensity polarizable continuum method (SCI-PCM) and MP2 PCM continuum methods have been used to calculate the effect of solvation on geometries and relative energies of the species involved in the 1,5-hydride shift. It is found that relative energies of acyclic and mu-hydrido-bridged carbocation structures as well as the energy barriers for 1,5-hydride shifts are in accord with experimental data if solvation effects are taken into account.
authors.affiliation: Faculty of Pharmacy and Biochemistry, University of Zagreb, 10000 Zagreb, Croatia.
authors.forename: Valerije
authors.initials: V
authors.lastname: Vrcek
authors.forename: Ivana
authors.initials: I
authors.lastname: Vinkovic Vrcek
authors.forename: Hans-Ullrich
authors.initials: HU
authors.lastname: Siehl
mesh_terms: D000478:Alkylation; D002412:Cations / Q000737:chemistry*; D006838:Hydrocarbons / Q000737:chemistry*; D008958:Models, Molecular; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry
chemical_list: D002412:Cations; D006838:Hydrocarbons; D012997:Solvents