The syntheses of alkali and earth alkaline dinitropyrazolate (DNP), trinitropyrazolate (TNP), and trinitroimidazolate (TNI) salts are reported. Additionally, copper trinitroimidazolate was synthesized. Their characterization by NMR spectroscopy, mass spectrometry, elemental analysis, and vibrational spectroscopy is reported as well. Crystal structures of compound Ba(DNP) 2 (9), which crystallizes with one molecule of methanol and ethyl ether as well as of compounds Sr(TNP) 2 ·3H 2 O (12), Ba(TNP) 2 ·3H 2 O (13), and LiTNI·3H 2 O (14) were determined. The energetic and thermal properties were measured * Prof. Dr. T. M. Klapötke

Unambiguously confirmed by low‐temperature in situ NMR experiments, X‐ray diffraction and vibrational spectroscopy, phosphonium‐carbenium superelectrophiles are shown to be generated in strong acidic conditions. Representing crucial intermediates, their exploitation allows for the synthesis of unprecedented fluorinated (cyclic) phosphine oxides.

Unambiguously confirmed by low-temperature in situ NMR experiments,X -rayd iffraction and vibrational spectroscopy, phosphonium-carbenium superelectrophiles are shown to be generated in strong acidic conditions.R epresenting crucial intermediates,t heir exploitation allows for the synthesis of unprecedented fluorinated (cyclic) phosphine oxides.Fluorinated compounds [1] are undeniably associated with the development of catalysis, [2] agrochemicals and drugs. [3] Organophosphorus compounds have found wide application in various fields such as catalysis,medicinal chemistry,material science and inorganic chemistry. [4] To our knowledge,t he formation of fluorinated phosphines and their derivatives via direct addition is limited to af ew reactions:t he trifluoromethylfluorosulfonylation, [5] theb romodifluoromethylation [6] of allyldiphenyl phosphine oxide,the nucleophile mediated reaction of Ruppert-Prakash reagent (or perfluoroalkyltrimethylsilanes) with phosphites,o ra ddition of LiC 2 F 5 to chlorinated phosphine [7] and the unimolecular radical nucleophilic substitution reaction. [8] Although the addition of an element-hydrogen pair to an unsaturated CÀCb ond is as tandard direct strategy to functionalize am olecular skeleton, hydro-(hetero)element addition to allylic or propargylic phos-phorus containing derivatives is rather limited. [9] Thep H dependent stability and the prototropic isomerization of the corresponding phosphonium derivatives may be the reason for the difficulty to selectively add any species to these derivatives under acidic conditions. [10] To avoid undesired rearrangement, Berlin used polyphosphoric acid (115 %) at elevated temperatures to perform the intramolecular Friedel-Crafts reaction of allyltriphenyl phosphonium salts. [11] In situ formation of ad ication was postulated in this seminal contribution, whose hypothesis was recently reformulated by Va silyev and Stankevič (Scheme 1a). [12] Laali et al. [13] and Klumpp et al. [14] went astep further by,respectively,showing the protonation of tetraphosphocubane and ketophosphonium salts in superacids. [15] On this basis,w ep ostulated that the generation of as uperelectrophile from an unsaturated organophosphorus compound can be expected under superacidic conditions and further exploited to produce valuable and innovative (P,F)-derivatives.W er eport here the first example of ahydrofluorination [16] and cyclization/fluorination of unsaturated phosphine oxides.T he involvement of phosphonium-carbenium superelectrophiles (Scheme 1b)i se videnced by X-ray crystallography,l ow-temperature NMR spectroscopy and DFT calculations.This work aims to address two important challenges: 1) Thed eactivation of the unsaturation after protonation of the P-containing function, which could prevent substrates from any reaction, needs to be outweighed by the high acidity Scheme1. a) Postulated and reported phosphorus containing polycations formation in acidic conditions(literature);b)Exploitation of phosphonium-carbeniumsuperelectrophiles for the synthesis of...