Chemical bonding in oxohalides of hypercoordinate nitrogen and phosphorus

• Published in: International journal of quantum chemistry Vol. 60; no. 1; pp. 393 - 400
• Main Authors: Cunningham, Terence P., Cooper, David L., Gerratt, Joseph, Karadakov, Peter B., Raimondi, Mario
• Format: Journal Article
• Language: English
• Published: New York John Wiley & Sons, Inc 05.10.1996
• ISSN: 0020-7608; 1097-461X
• DOI: 10.1002/(SICI)1097-461X(1996)60:1<393::AID-QUA38>3.0.CO;2-C

Spin‐coupled calculations are carried out for the nitryl halides FNO2 and CINO2. The picture that emerges suggests that the nitrogen atoms use all five valence electrons in covalent bonding. The description of the NO2 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 FPO2. We assess the geometries, charge distributions, and dipole moments of various X3NO and X3PO species (X = H, CH3, or F). We propose a simple rationalization of the dipole moment data without invoking supposed dπ‐pπ bonding. © 1996 John Wiley & Sons, Inc.