Salze von Halogenophosphorsäuren. XVI. ³¹P‐NMR‐Untersuchungen an 1,2‐Difluoro‐thiodiphosphaten

Abstract

Bei langsamer Hydrolyse von K2[P2S5F2] in Acetonitril wird der Schwefel schrittweise durch Sauerstoff ersetzt, wobei das 1,2‐Difluoro‐(thio)diphosphat‐Gerüst erhalten bleibt. Von den entstehenden 1,2‐Difluoro‐oxothiodiphosphaten wurden die chemischen Verschiebungen und die Kopplungskonstanten aus den 31P‐NMR‐Spektren bestimmt.

Synthesis and characterisation of trimethylsilyl phosphorohalidates: Me3SiOP(O)FX (X = Cl, Br) and (Me3SiO)2P2O3F2

“…In contrast to the reaction with POFCl 2 , this reaction proceeds quite quickly and according to 19 F and 31 P NMR spectroscopy, the bromidofluoridate 1b À70.4 d À38.3 dm 1015 1 JðPFÞ 6.7 2 JðP a P b Þ 3.5 3 JðP b F a Þ a AA 0 XX 0 spin system. b To ensure a consistence with the most literature data, 1 JðPFÞ are given as positive, though their absolute sign is always negative [38].…”

“…The 19 F NMR spectrum of 3 consists of two doublets at À70.9 and À71.1 ppm, both with the same intensities and exactly the same separation (970 Hz) of lines as in the 31 P NMR spectrum. All lines are broadened (w 1=2 ¼ 30 Hz) and the expected fine structure of an AA 0 XX 0 spectrum is not resolved.…”

“…However, a band shape analysis and simulation of spectrum gave coupling constants that compare well with those of the [P 2 O 5 F 2 ] 2À ion ( Table 3). The NMR parameters of [P 2 O 5 F 2 ] 2À were re-determined in the present study because the literature data [18,19] showed considerable differences in the magnitudes of 2 JðPP 0 Þ (2.5 and 17.1 Hz). The established value 13.6 Hz is commensurable with magnitudes of both 2 JðPPÞ constants (12.1 and 14.5 Hz) reported for the anion [FPO 2 OPO 2 OPO 3 ] 4À [20].…”

“…The NMR spectra were recorded on a Bruker DPX300 spectrometer ( 1 H NMR 300 MHz, 19 29 Si NMR, CFCl 3 for 19 F NMR and 85% H 3 PO 4 for 31 P NMR as external standards with negative shifts being upfield from the reference signal. Raman spectra were recorded on a Bruker Equinox IFS 55/S apparatus connected with Raman adapter FRA 106/S and using Nd:YAG-Laser (l ¼ 1064 nm).…”