Thermal decomposition of 4-fluorobenzenediazonium perfluoroorganyl(fluoro)borates, [4-FC6H4N2]Y (Y = RFBF3 (RF = C6F5, C6F13, trans-C4F9CFCF, cis-C6F13CFCF, CF3CC) and (C6F13)2BF2)

•Fluorodediazotation of 4-F-benzenediazonium perfluoroorganylfluoroborate salts, an until now unknown example of the Balz-Schiemann reaction type.•Preferred transfer of fluoride over the perfluoroorganyl nucleophile in the dediazotation of 4-F-benzenediazonium perfluoroorganylfluoroborate salts.•Isomerization of (C6F13)2BF to C6F13CF(BF2)C5F11 under acidic and thermal conditions.

Heating of the neat salts [4-FC6H4N2][RFBF3] (RF = C6F5, C6F13, trans-C4F9CFCF, cis-C6F13CFCF, CF3CC) or in solid mixtures with NaF gives the principal product 1,4-C6F2H4 besides RFBF2or Na[RFBF3], respectively. Thermolysis of [4-FC6H4N2][(C6F13)2BF2] in NaF results in 1,4-C6F2H4, Na[BF4], Na[(C6F13)2BF2], and a new type of product, the isomer Na[C6F13CF(BF3)C5F11].

Graphical abstractHeating of the neat salts [4-FC6H4N2][RFBF3] or in solid mixtures with NaF gives the principal product 1,4-C6F2H4 besides RFBF2 or Na[RFBF3], respectively. Thermolysis of [4-FC6H4N2][(C6F13)2BF2] in NaF results in 1,4-C6F2H4, Na[BF4], Na[(C6F13)2BF2], and a new type of product, the isomer Na[C6F13CF(BF3)C5F11].Figure optionsDownload full-size imageDownload as PowerPoint slide