35Cl Nqr spectroscopy of the [PO2Cl2]? and POCl3 groups in Me(PO2Cl2)2·2D (Me = Mg,Ca, Mn; D = POCl3,CH3COOC2H5,CH3COCH3) |
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| Authors: | W Fichtner Alarich Weiss |
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| Institution: | Institut für Physikalische Chemie, Physikalische Chemie III, Technische Hochschule Darmstadt, Petersenstrasse 20, D-6100 DarmstadtW. Germany |
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| Abstract: | 35Cl NQR spectra of dichlorophosphates Me(PO2Cl2)2 · 2D (Me = Mg, Ca, Mn; D = CH3COOC2H5, CH3COCH3, POCl3) are studied in the temperature range 77 ? T (K) ? 305. It is shown that the three compounds with CH3COOC2H5 as donor are isomorphic at 77 K, the crystal structure of Mn(PO2Cl2)2· 2CH3COOC2H5. The structure of Mg(PO2Cl2)2?· 2CH3COCH3 and of Mg(PO2Cl2)2 · 2POCl3 probably consists of infinite chains as found for Mn(PO2Cl2)2· 2CH3COOC2H5. Mg(PO2Cl2)2· 2CH3COOC2H5 shows phase transformations and a complicated dynamical behaviour leading to strong deviations from a Bayertype NQR function v = f(T). The donor capacity of POCl3 in Mg(PO2Cl2)2· 2POCl3 is comparable with the donor strength in AsCl3 · POCl3 · A dπ-pπ overlap of the P-O bond influences the P-Cl bond. |
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