Structure, magnetizability, and nuclear magnetic shielding tensors of bis-heteropentalenes. IV. Dihydrophospholophosphole isomers

• Published in: Journal of computational chemistry Vol. 27; no. 3; pp. 344 - 351
• Main Authors: Cuesta, Inmaculada García, Sánchez De Merás, Alfredo M. J., Lazzeretti, Paolo
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc., A Wiley Company 01.02.2006; Wiley Subscription Services, Inc
• Subjects: Chemical compounds; Comparative studies; DFT geometry; diatropicity; Geometry; GIAO magnetic properties; heteropentalenes; Magnetism; Molecular structure; NMR; Nuclear magnetic resonance
• ISSN: 0192-8651; 1096-987X
• DOI: 10.1002/jcc.20349

The geometry of the heteropentalenes formed by two phosphole units has been determined at the DFT level. The magnetic susceptibility and the nuclear magnetic shielding at the nuclei of these systems have also been calculated using gauge‐including atomic orbitals and a large Gaussian basis set to achieve near Hartree–Fock estimates. A comparative study of the various isomers, of their flattened analogs, and of the parent phosphole molecule, shows that the [3,4‐c] isomer is the most aromatic system in the set considered, assuming diatropicity and degree of planarity as indicators, even if it is the less stable in terms of total molecular energy. Plots of magnetic field‐induced current densities confirm diatropicity of P‐containing bis‐heteropentalenenes, showing, however, significant differences from the analogous systems with distinct heteroatoms. The maps give evidence of spiral flow nearby CC bonds, compatible with prevalent distortive behavior of π electrons exalted by pyramidalization at P, and competing against the σ electron compression, which would favor planar structure. © 2005 Wiley Periodicals, Inc. J Comput Chem 27: 344–351, 2006