[(C₆F₅)₂IF₂][BF₄], the First Salt with the Electrophilic Cation [(C₆F₅)₂IF₂]⁺: Synthesis, Reactivity, and Structure

Abstract

The substitution of hypervalently bonded fluorine atoms in C 6 F 5 IF 4 was performed with C 6 F 5 BF 2 and resulted in the new salt [(C 6 F 5 ) 2 IF 2 ][BF 4 ]. The iodonium(V) salt was characterized by multi-NMR and Raman spectroscopy and X-ray crystal structure analysis. The fluorinating ability of the new electrophilic cation [(C 6 F 5 ) 2 IF 2 ] ϩ was exemplified in reactions with monovalent iodine compounds (C 6 F 5 I, p-FC 6 H 4 I, and I 2 ) and with electron-poor

Polyvalent perfluoroorgano- and selected polyfluoroorgano-halogen(III and V) compounds

“…As an alternative to elemental fluorine, the following fluorinating agents can be used for the conversion of R F I to R F IF 2 : XeF 2 (R F = C 3 F 7 [17], C 4 F 9 [18], CF 3 CH 2 [18,19], C 6 F 5 [17,20], 2,3,5,6-C 5 F 4 N [21]) [C 6 F 5 XeF 2 ] + (R F = C 6 F 5 [22]), ClF (R F = C 6 F 5 [10]), ClF 3 (R F = C 2 F 5 , n-and i-C 3 F 7 , C 4 F 9 , C 6 F 13 , C 10 F 21 [6,23,24]; BrF 3 (R F = C 4 F 9 [6,24]), C 6 F 5 BrF 2 (R F = C 6 F 5 [10]), BrF 5 (R F = C 2 F 5 , C 4 F 9 [6,24]), C 6 F 5 BrF 4 (R F = C 6 F 5 [10]), and [(C 6 F 5 ) 2 IF 2 ] + (R F = C 6 F 5 [25,26]). The action of halogen fluorides often results in a mixture of R F IF 2 and R F IF 4 , and it was difficult to optimise the reaction conditions for the preparation of pure products.…”

“…Starting from C 6 F 5 IF 4 one fluorine of the 5c-8e hypervalent IF 4 group can be substituted by an aryl group Ar (Ar = C 6 F 5 , FC 6 H 4 ) (Eq. (55)) [26]. (Eq.…”

“…More different types are known with a C 6 F 5 group bonded to Hal(III and V). Besides the molecules C 6 F 5 IF 2 [10], C 6 F 5 IF 4 [80], C 6 F 5 I(OC(O)CF 3 ) 2 [134], and C 6 F 5 I(OC(O)C 6 F 5 ) 2 [135] (Table 2) salts with the cations [(C 6 F 5 ) 2 I] + [65] and [(C 6 F 5 ) 2 IF 2 ] + [26,113] were structurally characterised as well as bromonium salts with the related [(C 6 F 5 ) 2 Br] + cation [86] (Table 3). In case of CF 3 IX 2 molecules, CF 3 IF 2 shows the shortest average C-I distance and CF 3 ICl 2 the longest.…”

“…Partially positively charged iodine in C 6 F 5 I was fluorinated, even in the presence of the basic solvent MeCN, which principally reduces the oxidation potential by coordination and charge transfer (Eq. (95)) [26] …”

One‐Pot Synthesis of Isoquinolinium Salts by Rhodium‐Catalyzed CH Bond Activation: Application to the Total Synthesis of Oxychelerythrine

“…The 19 F and 11 B NMR spectral data of the tetrafluoroborate anion are in agreement with those reported previously. [10] To the best of our knowledge, this is the first report for the synthesis of isoquinolinium salts by catalytic CÀH activation.…”