The 4-(pentafluorosulfanyl)benzenediazonium tetrafluoroborate was synthesized and isolated as a stable salt for the first time.  A series of novel SF5-bearing alkenes, alkynes, and biaryl derivatives were synthesized by employing Heck-Matsuda, Sonogashira, and Suzuki coupling protocols. Dediazoniation with TMSX (X = Hal; N3; and CN) and NH4SCN in [BMIM][BF4] as solvent furnished the corresponding p-SF5-C6H4X derivatives. The azide derivative p-SF5-C6H4N3 entered into click-chemistry with phenylacetylenes to furnish the corresponding triazoles. The 4,4'-bis(pentafluorosulfanyl)biphenyl was synthesized by homo-coupling using  Pd(OAc)2. The corresponding azo-compounds were obtained through azo-coupling with reactive aromatic nucleophiles (1,3-dimethoxybenzene, 1,3,5-trimethoxybenzene, 1,2,4-trimethoxybenezene, aniline and phenol).  Fluorodediazoniation in [BMIM][PF6] and [BMIM][BF4] selectively furnished the fluoro-derivative p-SF5-C6H4F. Dediazonation in [BMIM][NTf2] gave p-SF5-C6H4OS(O)(CF3)=NSO2CF3 as major and p-SF5-C6H4-NTf2 as minor products.  Homolytic dediazoniation in MeCN/NaI gave the unsymmetrical biaryls p-SF5-C6H4-Ar (ArH = mesitylene and p-Xylene) along with p-SF5-C6H4I. Analysis of the dediazoniation product mixtures indicated that dediazonation of p-SF5-PhN2+ BF4- in low nucleophilicity, highly ionizing, solvents (TfOH, TFE, HFIP, TFAH) is mainly heterolytic, while in MeOH it is mainly homolytic. The isodesmic reaction p-SF5-C6H4+ + R-C6H5 � SF5-C6H5 + p-R-C6H4+ (with R = NO2, CF3, H) was gauged by DFT at various levels and by PCM.

4-(Pentafluorosulfanyl)benzenediazonium tetrafluoroborate: A versatile launch pad for the synthesis of novel aromatic SF<sub>5</sub> compounds via cross coupling, azo-coupling, homocoupling, dediazoniation, and click chemistry

247th National Meeting (2014)

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4-(Pentafluorosulfanyl)benzenediazonium tetrafluoroborate: A versatile launch pad for the synthesis of novel aromatic SF5 compounds via cross coupling, azo-coupling, homocoupling, dediazoniation, and click chemistry

4-(Pentafluorosulfanyl)benzenediazonium tetrafluoroborate: A versatile launch pad for the synthesis of novel aromatic SF₅ compounds via cross coupling, azo-coupling, homocoupling, dediazoniation, and click chemistry