A widely varying range of products in reactions of C6F5BrF2, C6F5IF2, and C6F5IF4 with Lewis acids of different strength

Bis(perfluoroorganyl)bromonium salts [(RF)2Br]Y (RF=aryl, alkenyl, and alkynyl)

“…The latter was not detected by 19 F NMR spectroscopy even at low temperature and local excess of BrF 3 (addition of neat BrF 3 to a diluted solution of R F BF 2 ) or stoichiometric excess of BrF 3 (BrF 3 :R F BF 2 = 1:1). Furthermore, reaction mixtures obtained from BrF 3 and C 6 F 5 BF 2 in weakly coordinating solvents did not contain products of the acid-assisted decomposition of C 6 F 5 BrF 2 (C 6 F 5 Br, bromoperfluorocycloalkenes C 6 BrF 7 and C 6 BrF 9 ) which occurred at À80 to À30 8C [25]. Hence, the rate of reaction of R F BrF 2 with R F BF 2 (step B) exceeds both: the rate of formation of R F BrF 2 (step A) and the rate of the acid-assisted decomposition of the latter.…”

“…(17)). Previously we have found that 17 is the major product of the BF 3 ÁNCCH 3 assisted decomposition of C 6 F 5 BrF 2 in CH 2 Cl 2 /MeCN [25].…”

“…The 11 B and 19 F NMR spectra showed the formation of K[C 2 F 5 CFBrCF 2 BF 3 ] (0.10 mmol, 15%). (25). 19 F NMR (CCl 2 FCClF 2 , 24 8C): d À75.9 (qdd, 5 J(F 1 , F 4 ) = 5 Hz, 4 J(F 1 , F 3A ) = 8 Hz, 4 J(F 1 , F 3B ) = 12 Hz, 3F, F 1 ), À79.0 (qd, 5 J(F 4 , F 1 ) = 5 Hz, 4 J(F 4 , F 2 ) = 11 Hz, 3F, F 4 ), À116.6 (qdd, 4 J(F 3A , F 1 ) = 8 Hz, 3 J(F 3A , F 2 ) = 8 Hz, 2 J(F 3A , F 3B ) = 286 Hz, 1F, F 3A ), À118.1 (qdd, 4 J(F 3B , F 1 ) = 12 Hz, 3 J(F 3B , F 2 ) = 10 Hz, 2 J(F 3B , F 3A ) = 286 Hz, 1F, F 3B ), À140.9 (qt, 4 J(F 2 , F 4 ) = 11 Hz, 3 J(F 2 , F 3 ) = 9 Hz, 1F, F 2 ) (lit.…”

New types of asymmetrical bromonium salts [RF(RF′)Br]Y where RF and/or RF′ represent perfluorinated aryl, alkenyl, and alkynyl groups

“…(18) can be assigned to a parallel reaction channel, the acid-assisted decomposition of C 6 F 5 BrF 2 to C 6 F 5 Br and unsaturated cyclic bromocontaining compounds described in Ref. [23].…”

“…We have found that bromane 1 reacted with the adduct CF 3 CCBF 2 ÁNCCH 3 (22) (1 equiv.) in PFP/MeCN to yield trifluoroprop-1-yn-1-yl(pentafluorophenyl)bromonium tetrafluoroborate (23), but the conversion of 22 was incomplete and in particular the main product was C 6 F 5 Br (molar ratio 23:17 5 5 1:4) (Eq. (20))…”