Chemical bonding in oxohalides of hypercoordinate nitrogen and phosphorus

✍ Scribed by Terence P. Cunningham; David L. Cooper; Joseph Gerratt; Peter B. Karadakov; Mario Raimondi

• Publisher: John Wiley and Sons
• Year: 1996
• Tongue: English
• Weight: 689 KB
• Volume: 60
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/(sici)1097-461x(1996)60:1<393::aid-qua38>3.0.co;2-c

✦ Synopsis

Spin-coupled calculations are carried out for the nitryl halides FNO, and ClNO,. The picture that emerges suggests that the nitrogen atoms use all five valence electrons in covalent bonding. The description of the NO, group appears to be essentially transferable between the two molecules. No evidence is found for active d-orbital participation in the bonding in either of these molecules or in FPO,. We assess the geometries, charge distributions, and dipole moments of various X,NO and X,PO species (X = H, CH,, or F). We propose a simple rationalization of the dipole moment data without invoking supposed d,-p, bonding. 0 1996 John Wiley & Sons, Inc. may be considered highly reactive derivatives of nitric acid, are also known and FONO has been studied in inert gas matrices. Chlorine nitrate is particularly important in the atmosphere, where it acts as a "temporary reservoir'' for active chlorine species implicated in ozone-layer depletion. The nitryl halides FNO, and C1N02 are reactive gases and powerful oxidizing agents. Although also an oxidizing gas, trifluoroamine N-oxide has been *To whom correspondence should be addressed.