Donorstabilized Monometaphosphates and Phosphonates- Structure,Bonding, and Reactivity |
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| Authors: | Manfred Meisel Annegrit Rabis Arnd-Rüdiger Grimmer Irmgard Hartwich Regina Bienert Dirk Wulff-molder |
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| Institution: | Humboldt-Universit?t zu Berlin, Institut für Chemie , D-10115 , Berlin , Germany |
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| Abstract: | Abstract Previoudy we reported on the preparative use of donorstabilized monometaphosphates, Py.PO2Cl and Py.PS2Cl1]. 3P MAS investigations as well as X-ray single crystal analysis have been carried out. The isotropic chemical shift of the sulfur compound shows the typical downfield shift (106 ppm) with respect to the oxygen compound The chemical shift anisotropy gives additional information. The relative large spans ω (Py.PO2Cl: 401 ppm, Py.PS2Cl: 461 ppm) 2] reveal strong deviations from tetrahedral symmetry (ω = 0 ppm) in agreement with the structural data. The values of the skew parametem K (0.64 and 0.71 resp.) reflect the trend to axial symmetry (k = ± l). X-ray diffraction and NMR data suggest a structural model corresponding to a concentration of double bond character on the two P-X bonds. This model is consistent with the extremely short P-X bond length (1.449 Å and 1.921 Å rasp.) as well as the large P-X-P bond angles (126.4°and 123.7° resp.). |
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