CHEMICAL BONDING IN OXOHALIDES OF HYPERCOORDINATE NITROGEN AND PHOSPHORUS

Spin-coupled calculations are carried out for the nitryl halides FNO2 and CINO2. The picture that emerges suggests that the nitrogen atoms u se all five valence electrons in covalent bonding. The description of the NO2 group appears to be essentially transferable between the two m olecules. No evidence is found for active d-orbital participation in t he bonding in either of these molecules or in FPO2. We assess the geom etries, charge distributions, and dipole moments of various X(3)NO and X(3)PO species (X = H,CH3, or F). We propose a simple rationalization of the dipole moment data without invoking supposed d(pi)-p(pi) bondi ng. (C) 1996 John Wiley & Sons, Inc.