Difluorophosphate des Aluminiums, Galliums und Zinks

Abstract

Al(PO2F2)3, Ga(PO2F2)3 und Zn(PO2F2)2 · 2 HOP(O)F2 werden durch Umsetzung von AlCl3, GaCl3, bzw. ZnCl2 mit Difluorophosphorsäure dargestellt. Die physikalischen Eigenschaften und IR‐Spektren der Verbindungen dienen zur Ableitung von Strukturvorschlägen. Für Al(PO2F2)3) und Ga(PO2F2)3 können polymere Strukturen angenommen werden. In Zn((PO2F2)2 2 HOP(O)F2 sind die Säuremoleküle über den terminalen Sauerstoff an das Metallatom gebunden.

Crystal Structures of [Bu2Sn(O2PPh2)2], [Ph2Sn(O2PPh2)2], and [PhClSn(O2PPh2)OMe]2. Raman Spectra of [Ph2Sn(O2PPh2)2] and [PhClSn(O2PPh2)OMe]2

“…The formation of [PhClSn(O 2 PPh 2 )OMe] 2 (3) indicates that Sn-Cl and Sn-C bonds of Ph 2 SnCl 2 are cleaved. In our previous studies on the reactions of HO 2 PMe 2 with Ph 2 SnCl 2 [4] as well as HO 2 PPh 2 with R 2 SnCl 2 (R ϭ Me [2], Et [3]), fission of only Sn-Cl bonds has been observed leading to the corresponding diorganotin bis(diorganophosphinates). Consequently, the Sn-Cl bonds are cleaved favorably compared to the Sn-C bonds in such acidolysis reactions.…”

“…We have found that crystals suitable for X-ray crystallographic studies can be isolated from the reactions of R 2 SnCl 2 with HO 2 PR 2 in methanol at ambient temperature. Accordingly, the crystal structures of [Me 2 [4] have been determined.…”

“…Keywords: Tin; Crystal structure; Raman spectra; Diphenylphosphinates; Methoxo bridges In these polymeric compounds the diorganophosphinate groups behave as bidentate bridges between the tin atoms leading to (SnOPO) 4 (3). The Raman spectra of 2 and 3 are given and discussed.…”

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].…”

“…These esters react with electrophilic metal chlorides, either forming donor-acceptor complexes via the terminal oxygen atom of the Me 3 SiOP(O)X 2 or giving covalent chloride-dihalogenophosphates under the cleavage of Si-O bonds [1][2][3]. On the other hand, treatment of Me 3 SiOP(O)F 2 with a nucleophilic halide or pseudohalide anion leads to the corresponding difluorophosphate [4].…”