When SF₅ outplays CF₃: effects of pentafluorosulfanyl decorated scorpionates on copper

Abstract

Polyfluorinated, electron-withdrawing, and sterically demanding supporting ligands are of significant value in chemistry. Here we report the assembly and use of a bis(pyrazolyl)borate, [Ph2B(3-(SF5)Pz)2]- that combines all such features, and involves...

Binding Interactions in Copper, Silver and Gold π‐Complexes

“… [13] Furthermore, bis‐ and tris‐(pyrazolyl)borate copper complexes [H 2 B(3,5‐(CF 3 ) 2 Pz) 2 ]CuNCMe and [HB(3,5‐(CF 3 ) 2 Pz) 3 ]CuNCMe are excellent catalysts for the cyclopropenation of alkynes, [4a] while [Ph 2 B(3‐(CF 3 ) 2 Pz) 2 ]Cu(C 2 H 4 ) mediates alkene cyclopropanation chemistry. [14] The copper complexes such as [HB(3,5‐(CH 3 ) 2 Pz) 3 ]Cu(C 2 H 4 ) with non‐fluorinated tris(pyrazolyl)borate ligand (Figure 1 ) supports are also proven to be good catalysts for the cyclopropanation of alkenes, cyclopropenation of alkynes, and aziridination of alkenes. [15]…”

Terminal and Internal Alkyne Complexes and Azide-Alkyne Cycloaddition Chemistry of Copper(I) Supported by a Fluorinated Bis(pyrazolyl)borate

“…It is, however, comparatively less effective than the related trinuclear copper catalyst {μ-[3,5-(CF 3 ) 2 Pz]Cu} 3 involving bridging pyrazolates. We are presently exploring the metal mediated alkene and alkyne chemistry supported by these and other fluorinated ligands [ 90 , 91 ].…”

Recent Advances in the Synthesis and Medicinal Chemistry of SF5 and SF4Cl Compounds

“…The first SF5-decorated scorpionate [Ph2B(3-(SF5)Pz)2] − was recently described, and some of its copper chemistry was exploited to test the cyclopropanation of styrene with ethyl diazoacetate and CF3CHN2. 70 71 The authors detected an important difference of reactivity between perfluoroalkyl iodides, which typically form (poly)perfluoroalkylfullerenes upon heating, and the SF5CF2CF2I reagent, which produced three types of products, cycloadducts C60(c-C2F4)n, pentafluorosulfanyl products C60(CF2CF2SF5)m, and the mixed derivatives C60(C2F4)n(CF2CF2SF5)m. The product distribution in the reactions with SF5CF2CF2I was found to be highly sensitive to the reaction temperature, however improved selectivity for the bis-adduct 1,7-C60(CF2CF2SF5)2, which was isolated and spectroscopically characterized, was achieved by optimization of the reaction conditions, especially a reaction temperature in the range 140-150 °C. Reactions between C60 and SF5CF2I were also tested, resulting in the formation of a mixture of derivatives with the general formula C60(CF3)n(CF2SF5)m.…”

“…Scheme 77 Synthesis of [Ph2B(3-(SF5)Pz)2]Cu(C2H4)70 SF5-functionalized fullerenes were obtained by Boltalina et al by reacting fullerene C60 with SF5CF2CF2I and SF5CF2I in the presence of Cu powder at 140-180 °C 71. The authors detected an important difference of reactivity between perfluoroalkyl iodides, which typically form (poly)perfluoroalkylfullerenes upon heating, and the SF5CF2CF2I reagent, which produced three types of products, cycloadducts C60(c-C2F4)n, pentafluorosulfanyl products C60(CF2CF2SF5)m, and the mixed derivatives C60(C2F4)n(CF2CF2SF5)m. The product distribution in the reactions with SF5CF2CF2I was found to be highly sensitive to the reaction temperature, however improved selectivity for the bis-adduct 1,7-C60(CF2CF2SF5)2, which was isolated and spectroscopically characterized, was achieved by optimization of the reaction conditions, especially a reaction temperature in the range 140-150 °C.…”