- C6F5XeY Molecules (Y = F and Cl): New synthetic approaches. first structural proof of the organoxenon halide molecule C 6F5XeF
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The arylxenonium salt [C6F5Xe][BF4] reacts with different sources of nucleophiles, Y (naked fluoride, [N(CH 3)4]F, the silanes, (CH3)3SiCl and (C2H5)3SiH, and the cadmiumorganyl, Cd(C 6F5)2), in coordinating solvents (C 2H5CN, CH3CN, CD3CN). While the products C6F5XeF, C6F5XeCl, and (C6F5)2Xe are well defined molecules, in reactions with (C2H5)3SiH only decomposition products presumably derived from 6F5XeH6F5XeC2H56F5XeF are discussed.
- Bilir, Vural,Frohn, Hermann-Josef
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p. 505 - 512
(2013/09/23)
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- Reactions of fluoroalk-1-en-1-yltrifluoroborate and perfluoroalk-1-yn-1- yltrifluoroborate salts and selected hydrocarbon analogues with hydrogen fluoride and with halogenating agents in aHF and in basic solvents
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The relative rate of the electrophilic hydrodeboration of K[R′BF 3] with HF (27-100%) diminishes in the series R′ = C 4H9CC > C4F9CFCFCC > CF 2C(CF3) > C3F7CC ～ (CF 3)2CFCC > CF3CC. When R′ = CF 3CC the new salt K[CF3CH2-CF2BF 3] was obtained by addition of HF besides CF3CCH and K[BF4]. Small amounts of water caused the formation of K[CF 3CH2-C(O)BF3] as a by-product. The electrophilic halofluorination of perfluoroalkenyltrifluoroborate salts with NCS or NBS in aHF (anhydrous HF) led to K[RFCFHal-CF2BF 3] (from K[RFCFCFBF3]) and K[R FCHal2-CF2BF3] (from K[R FCHalCFBF3] and K[RFCCBF3]) (Hal = Cl, Br). Treatment of K[RFCFCFBF3] and K[R FCCBF3] with 5% F2/N2 in MeCN gave the corresponding salts K[RFCF2-CF2BF 3] in 16-25% isolated yield. Reactions of K[trans-C4F 9CFCFBF3] with Cl2 in MeOH resulted in K[C 4F9CFCl-C(O)BF3] (major product). The latter was also obtained in reactions of K[trans-C4F9CFCFBF 3] with Cl2 in MeCN or sulfolane after sequential methanolysis of the primarily formed products. In contrast, the salts K[RCFCFBF3] (R = CnF2n+1, trans-C 4H9) and K[CF3CCBF3] underwent bromodeboration to RCFCFBr and CF3CCBr, respectively, when they were reacted with bromine in the polar solvents MeOH, MeCN, or sulfolane.
- Bardin, Vadim V.,Adonin, Nicolay Yu.,Frohn, Hermann-Josef
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experimental part
p. 114 - 128
(2012/04/10)
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- Anodic and cathodic reactions in acetonitrile/tetra-n-butylammonium tetrafluoroborate: an electrochemical and infrared spectroelectrochemical study
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In situ infrared spectroelectrochemistry has been used to be observe electrolyte/solvent breakdown processes in TBAF/acetonitrile at a platinum electrode.Anodic breakdown gives the adduct CH3CNBF3 as the major product.Cathodic breakdown gives the anion of 3-aminocrotonitrile as the major product in the absence of water, and the formation of this product is a consequence of reduction of hydrogen dissolved in the metal.In the presence of water the anion of acetamide is also formed, and breakdown commences at much less negative potentials.
- Foley, John K.,Korzeniewski, Carol,Pons, Stanley
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p. 201 - 206
(2007/10/02)
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