HALOGEN SUBSTITUTION AT PHOSPHORUS IN PHOSPHAALKENES AND PHOSPHASILENES VERSUS BIS(METHYLENE)PHOSPHORANES - A QUANTUM-CHEMICAL EVALUATION OF BONDING PROPERTIES

Schoeller W, STRUTWOLF J, TUBBESING U, BEGEMANN C (1995)
JOURNAL OF PHYSICAL CHEMISTRY 99(8): 2329-2334.

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Abstract
The bonding properties of/at phosphorus-halogen substituted (F, Cl, Br, I) phosphaalkenes and -silenes were explored with ab initio calculations 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 pair X(-)PCH(2)(+). This is substantiated by an analysis of the natural atomic orbital populations. They evidence a strong shift of electron density from phosphorus toward the electronegative halogen atom in the a-space, with negligible pi-mesomeric interaction of the lone pair at the halogen with the PC sc-bond. A similar but slightly less affirmed situation 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 symmetry reduction from C-2v to C-2 symmetry. d-orbital participation at phosphorus does not play any role in bonding.
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Schoeller W, STRUTWOLF J, TUBBESING U, BEGEMANN C. HALOGEN SUBSTITUTION AT PHOSPHORUS IN PHOSPHAALKENES AND PHOSPHASILENES VERSUS BIS(METHYLENE)PHOSPHORANES - A QUANTUM-CHEMICAL EVALUATION OF BONDING PROPERTIES. JOURNAL OF PHYSICAL CHEMISTRY. 1995;99(8):2329-2334.
Schoeller, W., STRUTWOLF, J., TUBBESING, U., & BEGEMANN, C. (1995). 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), 2329-2334.
Schoeller, W., STRUTWOLF, J., TUBBESING, U., and BEGEMANN, C. (1995). HALOGEN SUBSTITUTION AT PHOSPHORUS IN PHOSPHAALKENES AND PHOSPHASILENES VERSUS BIS(METHYLENE)PHOSPHORANES - A QUANTUM-CHEMICAL EVALUATION OF BONDING PROPERTIES. JOURNAL OF PHYSICAL CHEMISTRY 99, 2329-2334.
Schoeller, W., et al., 1995. 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), p 2329-2334.
W. 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, vol. 99, 1995, pp. 2329-2334.
Schoeller, W., STRUTWOLF, J., TUBBESING, U., BEGEMANN, C.: HALOGEN SUBSTITUTION AT PHOSPHORUS IN PHOSPHAALKENES AND PHOSPHASILENES VERSUS BIS(METHYLENE)PHOSPHORANES - A QUANTUM-CHEMICAL EVALUATION OF BONDING PROPERTIES. JOURNAL OF PHYSICAL CHEMISTRY. 99, 2329-2334 (1995).
Schoeller, Wolfgang, STRUTWOLF, J, TUBBESING, U, and BEGEMANN, C. “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): 2329-2334.
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