HALOGEN SUBSTITUTION AT PHOSPHORUS IN PHOSPHAALKENES AND PHOSPHASILENES VERSUS BIS(METHYLENE)PHOSPHORANES - A QUANTUM-CHEMICAL EVALUATION OF BONDING PROPERTIES
Ww. Schoeller et al., HALOGEN SUBSTITUTION AT PHOSPHORUS IN PHOSPHAALKENES AND PHOSPHASILENES VERSUS BIS(METHYLENE)PHOSPHORANES - A QUANTUM-CHEMICAL EVALUATION OF BONDING PROPERTIES, Journal of physical chemistry, 99(8), 1995, pp. 2329-2334
The bonding properties of/at phosphorus-halogen substituted (F, Cl, Br
, I) phosphaalkenes and -silenes were explored with ab initio calculat
ions with effective core potential (ECP(d)) optimizing the geometries
at the RHF and CISD levels. Compared with the parent compounds HP=CH2
the PC bond is slightly shrunk, indicating the formation of an ion pai
r X(-)PCH(2)(+). This is substantiated by an analysis of the natural a
tomic orbital populations. They evidence a strong shift of electron de
nsity from phosphorus toward the electronegative halogen atom in the a
-space, with negligible pi-mesomeric interaction of the lone pair at t
he halogen with the PC sc-bond. A similar but slightly less affirmed s
ituation results for the P-halogen substituted phosphasilenes as well
as for the bis(methylene)phosphoranes. Furthermore, for the latter the
halogen substitution enforces a Jahn-Teller distortion, causing symme
try reduction from C-2v to C-2 symmetry. d-orbital participation at ph
osphorus does not play any role in bonding.