Salts of Tris(pentafluoroethyl)silylchalcogenolates [Si(C₂F₅)₃E]⁻ with E = S, Se, and Te: Synthesis, Structure, and Reactivity

Abstract

Unlike silanolates [SiR 3 O] − (R = alkyl, aryl), which have been intensely studied, the heavier derivatives [SiR 3 E] − (E = S, Se, Te) have been much less examined. Among such species, virtually nothing is known about perfluoroalkyl-substituted silylchalcogenolates. In this contribution, a convenient synthesis of tris(pentafluoroethyl)silylchalcogenolate salts [{(Et 2 N) 3 P N} 3 PN(H) t Bu][Si(C 2 F 5 ) 3 E] (E = S, Se, Te; t Bu = tert-butyl) is presented. All representatives were isolated and fully characterized by multinuclear NMR spectroscopy, IR spectroscopy, mass spectrometry, elemental analysis, and X-ray diffraction studies. Furthermore, first reactivity studies of these novel species toward selected metal halide complexes were performed. In this course, metal complexes [HgPh{SSi(C 2 F 5 ) 3 }] (2) and [Au(PPh 3 ){SSi(C 2 F 5 ) 3 }] (3) were isolated and characterized.

Synthesis and Properties of the Perfluoroethyl Martin Silicate: Reactivity in Solution and Solid‐State Mechanochemistry

“…The p-block elements-based derivatives bearing a strongly electron-withdrawing-C 2 F 5 moiety have recently emerged as promising tools for organic synthesis, with novel reactivities from an experimental and theoretical point of view. [1] Due to the strong Lewis acidity induced by the C 2 F 5 substituent on the central atom, access to the corresponding stable hypercoordinate phosphorus [2][3][4] or silicon [5][6][7][8][9][10] species has been reported. These species have been synthesized by addition of pentafluoroethyllithium [Li][C 2 F 5 ], obtained by metalation of the fluorinated gas HFC-125 (HC 2 F 5 ), onto the chlorinated P or Si substrate (Figure 1.a).…”