Spatial models of the current density field induced in the cyclopropane molecule by stationary, homogeneous magnetic fields, parallel to either the C3 or the C2 symmetry axis, have been constructed. A compact, abridged representation of the models is given via stagnation graphs that convey essential information. Maps of streamlines and moduli are also reported to complete current models that have proven useful to rationalize magnetic tensor properties, that is, magnetizability, 1H and 13C nuclear shieldings, and magnetic shielding along the C3 symmetry axis. Plots of Biot-Savart magnetic shielding density combined with current density visualization yield an accurate, detailed account of the shielding mechanisms. The magnetropicity of the system described by the current density model is fully consistent with the magnitude of magnetic tensors calculated at near Hartree-Fock level. In a field perpendicular to the molecular plane, cyclopropane sustains a diatropic ó-ring current with the following peculiar features: (i) it follows the molecular periphery rather than the CC framework; (ii) it bifurcates in the proximity of the methylene moieties flowing along the CH bonds, both above and below the óh plane; (iii) it has an effect on the values of response properties, although it is not as large as expected from naive arguments (e.g., the center-of-mass value of the magnetic shielding constant is dominated by in-plane components rather than the out-of-plane component, which is in contrast to ð-aromatic systems such as benzene); (iv) it has a negligible effect on the strong anisotropy of carbon magnetic shielding, which is shown to arise from local currents. No evidence for strong diatropism, and therefore ó-aromaticity of the cyclopropane molecule, was found on the magnetic criterion.

Assessment of sigma-Diatropicity of the Cyclopropane Molecule

ZANASI, Riccardo
2007

Abstract

Spatial models of the current density field induced in the cyclopropane molecule by stationary, homogeneous magnetic fields, parallel to either the C3 or the C2 symmetry axis, have been constructed. A compact, abridged representation of the models is given via stagnation graphs that convey essential information. Maps of streamlines and moduli are also reported to complete current models that have proven useful to rationalize magnetic tensor properties, that is, magnetizability, 1H and 13C nuclear shieldings, and magnetic shielding along the C3 symmetry axis. Plots of Biot-Savart magnetic shielding density combined with current density visualization yield an accurate, detailed account of the shielding mechanisms. The magnetropicity of the system described by the current density model is fully consistent with the magnitude of magnetic tensors calculated at near Hartree-Fock level. In a field perpendicular to the molecular plane, cyclopropane sustains a diatropic ó-ring current with the following peculiar features: (i) it follows the molecular periphery rather than the CC framework; (ii) it bifurcates in the proximity of the methylene moieties flowing along the CH bonds, both above and below the óh plane; (iii) it has an effect on the values of response properties, although it is not as large as expected from naive arguments (e.g., the center-of-mass value of the magnetic shielding constant is dominated by in-plane components rather than the out-of-plane component, which is in contrast to ð-aromatic systems such as benzene); (iv) it has a negligible effect on the strong anisotropy of carbon magnetic shielding, which is shown to arise from local currents. No evidence for strong diatropism, and therefore ó-aromaticity of the cyclopropane molecule, was found on the magnetic criterion.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11386/1659445
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