H.-J. Frohn, A. Wenda, U. Flörke
P(C6F5)3, As(C6F5)3, Sb(C6F5)3, and Bi(C6F5)3 was studied in
CH3CN at 20 °C. Solutions of tris(pentafluorophenyl)pnictane
compounds (a: P(C6F5)3 (105.8 mg; 0,20 mmol); b: As(C6F5)3
(98.5 mg; 0.17 mmol); c: Sb(C6F5)3 (106 mg; 0.17 mmol), or d:
Bi(C6F5)3 (76.6 mg; 0.108 mmol)) were each dissolved in CH3CN
(800 μl) at ambient temperature and added to four stirred solutions
of [(C6F5)2IF2][BF4] with admixtures of 4 % [(C6F5)2I][BF4] and
1 % [(C6F5)2IO][BF4] (a: 56 mg; 0.096 mmol; b: 56.6 mg;
0.096 mmol; c: 54.9 mg; 0.092 mmol, or d: 31.6 mg; 0.054 mmol)
each in CH3CN (400 μl). The reaction mixtures were monitored
periodically by 19F NMR spectroscopy. The conversion of
[(C6F5)2IF2][BF4] was completed after a: P(C6F5)3 30 min, b:
As(C6F5)3 10 min, c: Sb(C6F5)3 25 min, and d: Bi(C6F5)3 80 min.
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The 1 : 1 reaction of [(C6F5)2IF2][BF4] (0,160 mmol) with P(C6F5)3
(0,156 mmol) in 1.45 mL CH3CN proceeded very slowly and
showed the following molar composition after 1 h {P(C6F5)3 31 %,
[(C6F5)2IF2]ϩ 37 %, [(C6F5)2I]ϩ 21 % [BF4]Ϫ 60 %, (C6F5)3PF2
10 %} and after 120 h {P(C6F5)3 13 %, [(C6F5)2IF2]ϩ 22 %,
[(C6F5)2I]ϩ 26 %, [BF4]Ϫ 53 %, (C6F5)3PF2 19 %, C6F5I 9 %,
(C6F5)3PO 7 %, [(C6F5)4P]ϩ 4 %}.
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155Ϫ159.
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Zh. Org. Khim. 1972, 8, 210Ϫ211.
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1669Ϫ1679; b) F. M. Beringer, P. Bodlaender, J. Org. Chem.
1968, 33, 2981Ϫ2984.
[18] J. Helber, H.-J. Frohn, A. Klose, T. Scholten, Arkivoc 2003,
AV-682A/682.pdf
The reaction of [(C6F5)2IF2][BF4] with CsF
[19] H.-J. Frohn, V. V. Bardin, Organoxenonium Salts: Synthesis
by “Xenodeborylation“, Reactivities, and NMR Spectroscopic
Properties; in Recent Developments in Carbocation and Onium
Chemistry, K. K. Laali (Ed.), ACS Symp. Ser. 965, ACS,
Washington, 2007.
[20] H.-J. Frohn, N. LeBlond, K. Lutar, B. Zemva, Angew. Chem.
Int. Ed. 2000, 39, 391Ϫ393.
[21] F. Bailly, P. Barthen, H.-J. Frohn, M. Köckerling, Z. Anorg.
Allg. Chem. 2000, 626, 2419Ϫ2427.
[22] A. Abo-Amer, H.-J. Frohn, C. Steinberg, U. Westphal, J. Flu-
orine Chem. 2006, 127, 1311Ϫ1323.
[23] H.-J. Frohn, U. Westphal, unpubl. result, the fluoride affinity
was calculated on the B3LYP/LANL2DZ level.
[24] H.-J. Frohn, N. Y. Adonin, V. V. Bardin, Z. Anorg. Allg. Chem.
2003, 629, 2499Ϫ2508.
A
cold (Ϫ40 °C) solution of [(C6F5)2IF2][BF4] (81.7 mg;
0.139 mmol) in CH3CN (450 μl) which contained 2 %
[(C6F5)2I][BF4] and 4 % [(C6F5)2IO][BF4] was added to a cold
(Ϫ40 °C) suspension of CsF (213 mg; 1.40 mmol) in CH3CN
(150 μl). The progress of the reaction was monitored by 19F NMR
spectroscopy. After 20 min the mother liquor contained
[((C6F5)2IF2)2F][BF4] and [(C6F5)2I][BF4] (molar ratio: 91 : 9). The
solid residue was dissolved in water. 19F NMR confirmed the pres-
ence of FϪ and [BF4]Ϫ as the only F-containing compounds.
Acknowledgements. We gratefully acknowledge financial support by
the Fonds der Chemischen Industrie and the donation of chemicals
by Solvay and Honeywell.
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Chem. 2000, 598, 127Ϫ135.
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Z. Anorg. Allg. Chem. 2008, 764Ϫ770