ON THE ELECTRONIC-STRUCTURES OF THE METAPHOSPHATE (METAPHOSPHITE) ANIONS PX(3)((-))(PX(2)((-))), X=CH2, SIH2, NH, PH, O, S

Schoeller W, STRUTWOLF J, NIECKE E (1995)
THEOCHEM-JOURNAL OF MOLECULAR STRUCTURE 333(3): 249-260.

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Abstract
The structures of the metaphosphates (metaphosphites) PX(3)((-)))(PX(2)((-))), (X = CH2, SiH2, NH, PH, O, S) are investigated by means of ab initio calculations of double-zeta quality. For the cases X = CH2 and SiH2 a second-order Jahn-Teller distortion on the planar (D-3h) geometries is operative in the metaphosphate anions. It causes pyramidalization of the terminal groups (for X = CH2, SiH2) and the central phosphorus atom (for X = SiH2). The various types of symmetry distortions are accompanied by a weak alpha+pi bonding of the terminal ligands towards the central phosphorus atom. This matter is evidenced by an analysis of corresponding group transfer reactions. In contrast, for the cases X = NH, PH, O, S, planar structures (C-3h, D-3h) are adopted with formation of strong alpha+pi bonds of the central phosphorus towards the ligand atoms, again in accord with corresponding group transfer reactions. The vibrational analysis within the harmonic approximation reveals a decreasing tendency for pyramidalization at the central phosphorus atom, with increasing electronegativity of the ligand X. This is due to depletion of pi-electron density at the central atom. A silylene unit is more strongly bound in the tris(silylene))metaphosphate anion than in the silylene-phosphorane, according to corresponding group transfer reactions.
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Schoeller W, STRUTWOLF J, NIECKE E. ON THE ELECTRONIC-STRUCTURES OF THE METAPHOSPHATE (METAPHOSPHITE) ANIONS PX(3)((-))(PX(2)((-))), X=CH2, SIH2, NH, PH, O, S. THEOCHEM-JOURNAL OF MOLECULAR STRUCTURE. 1995;333(3):249-260.
Schoeller, W., STRUTWOLF, J., & NIECKE, E. (1995). ON THE ELECTRONIC-STRUCTURES OF THE METAPHOSPHATE (METAPHOSPHITE) ANIONS PX(3)((-))(PX(2)((-))), X=CH2, SIH2, NH, PH, O, S. THEOCHEM-JOURNAL OF MOLECULAR STRUCTURE, 333(3), 249-260.
Schoeller, W., STRUTWOLF, J., and NIECKE, E. (1995). ON THE ELECTRONIC-STRUCTURES OF THE METAPHOSPHATE (METAPHOSPHITE) ANIONS PX(3)((-))(PX(2)((-))), X=CH2, SIH2, NH, PH, O, S. THEOCHEM-JOURNAL OF MOLECULAR STRUCTURE 333, 249-260.
Schoeller, W., STRUTWOLF, J., & NIECKE, E., 1995. ON THE ELECTRONIC-STRUCTURES OF THE METAPHOSPHATE (METAPHOSPHITE) ANIONS PX(3)((-))(PX(2)((-))), X=CH2, SIH2, NH, PH, O, S. THEOCHEM-JOURNAL OF MOLECULAR STRUCTURE, 333(3), p 249-260.
W. Schoeller, J. STRUTWOLF, and E. NIECKE, “ON THE ELECTRONIC-STRUCTURES OF THE METAPHOSPHATE (METAPHOSPHITE) ANIONS PX(3)((-))(PX(2)((-))), X=CH2, SIH2, NH, PH, O, S”, THEOCHEM-JOURNAL OF MOLECULAR STRUCTURE, vol. 333, 1995, pp. 249-260.
Schoeller, W., STRUTWOLF, J., NIECKE, E.: ON THE ELECTRONIC-STRUCTURES OF THE METAPHOSPHATE (METAPHOSPHITE) ANIONS PX(3)((-))(PX(2)((-))), X=CH2, SIH2, NH, PH, O, S. THEOCHEM-JOURNAL OF MOLECULAR STRUCTURE. 333, 249-260 (1995).
Schoeller, Wolfgang, STRUTWOLF, J, and NIECKE, E. “ON THE ELECTRONIC-STRUCTURES OF THE METAPHOSPHATE (METAPHOSPHITE) ANIONS PX(3)((-))(PX(2)((-))), X=CH2, SIH2, NH, PH, O, S”. THEOCHEM-JOURNAL OF MOLECULAR STRUCTURE 333.3 (1995): 249-260.
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