Study on the aromaticity and reactivity of chlorophosphinines

✍ Scribed by László Nyulászi; György Keglevich

• Publisher: John Wiley and Sons
• Year: 1994
• Tongue: English
• Weight: 589 KB
• Volume: 5
• Category: Article
• ISSN: 1042-7163
• DOI: 10.1002/hc.520050209

✦ Synopsis

Aromaticity of phosphinine derivatives, such as 2-, 3-, and 4-chlorophosphinines and 4-chloro-3-methyland 3,5-dimethylphosphinine, has been investigated by means of quantum-chemical calculations and photoelectron spectroscopy. The position of the rr- bands in the phoi'oelectron spectra of 4-chloro-3methyl-and 3,5diinethylphosphinine indicated that the aromaticity of these species is similar to that of the corresponding benzene derivatives.

The MP2/6-31GQ and the HF/3-21G(") geometries of the chlorophosphinines, together with the isodesmic reaction energies and Mulliken charge distributions, showed that the electronic system of phosphinine is not significantly perturbed by the chbro-substitution .

3-methyl-4-chk1rophosphinine, similarly to 2chlorophosphinine, was inert toward nucleophiles even under forced conditions. This unreactivity can more likely be rationalized by kinetic considerations than by thermodynamic arguments (such as increased aromatic stabilization of the chlorophosphinines).