Selective Synthesis of Fluoro-, Fluorohydro-, and Chlorofluorosilanes from Hydrosilanes with the Use of a CuCl₂(CuI)/KF Reagent

Abstract

A selective synthesis of fluoro-, fluorohydro-, and chlorofluorosilanes from hydrosilanes has been examined. The reaction of Me2PhSiH and MePh2SiH with a mixture consisting of 2 equiv of CuCl2, 1 equiv of KF, and a catalytic amount of CuI in THF at room temperature afforded Me2PhSiF and MePh2SiF in high yields, respectively. With slight modification of this reaction, n-Hex2SiHF, Ph2SiHF, MeMesSiHF, MePhSiHF, PhSiH2F, and PhSiHF2 could be readily prepared from the corresponding polyhydrosilanes selectively in high yields. Treatment of MePhSiHF and Ph2SiHF with 2 equiv of CuCl2 in the presence of a catalytic amount of CuI afforded the respective chlorofluorosilanes, MePhSiClF and Ph2SiClF.

Convenient synthesis of alkoxyhalosilanes from hydrosilanes

“…However, the selectivity of substitution reactions at dihalo-and dialkoxysilanes is not always high, unless steric requirement prevents the second molecule of the nucleophile from approaching the silicon center [1]. Recently, we reported the synthesis of chlorofluorosilanes from selective and successive halogenation of dihydrosilanes [2]. As expected, their substitution reactions proceed selectively and only the Si-Cl bond is substituted upon interaction with 1 equiv.…”

Use of C,N-chelated triorganotin(IV) fluoride for fluorination of organic compounds, coordination compounds, phosphines, silanes and stannanes

“…The typical procedure is as follows: amount of 40 -200 mg of appropriate substrate was added to 6 at conditions summarized in Table 3 , and the mixture was stirred for 1 min (entry 12) up to 8 days (catalytic entry 9), the sample was fi ltered, in the case of heterogeneous reactions or paramagnetic species, and the solvent removed in vacuo (in the case of entries 9, 18 and 23 the products were trapped at liquid nitrogen temperature), then the deuterated benzene or chloroform was added and the composition and purity of material was checked by GC-MS and multinuclear NMR spectroscopy ( Damrauer and Simon , 1988;Kunai , et al, 1996 ;Lickiss and Lucas, 1996 ). The products can be separated by washing of 2 by pentane or by ( vacuo ) distillation, characterization of metal fl uorides was performed by powder X-ray diffraction methods.…”

Structure of C, N-chelated nButyltin(IV) fluorides and their use as fluorinating agents of some chlorosilanes, chlorophosphine and metal halides

“…In the case of chlorosilanes (Table 1) fluorination method seems to be very effective, hence a catalytic version was also attempted. Chlorosilanes can be transformed to appropriate fluorosilanes by several methods and reagents [14,15]: BF 3 ÁOEt 2 , SbF 3 , ZnF 2 , NH 4 F, CuF 2 , Na 2 SiF 6 , NaPF 6 , NaSbF 6 , NaBF 4 , Me 3 SnF, AgF, PF 5 , Ph 3 CBF 4 , SbF 3 , NOBF 4 , NO 2 BF 4 and CuF 2 /CCl 4 , but it is not very easy to obtain selectively fluorosilanes containing Si-H bond(s). Van Dyke et al made partially fluorinated polysilanes by PF 5 or Ph 3 CBF 4 methods.…”

“…The amount of 40-200 mg of appropriate substrate was added to 2 at conditions summarized in Table 1, and the mixture was stirred for 1 min (run 12) up to 8 days (catalytic run 9), the sample was filtered, in the case of heterogenous reactions or paramagnetic species, and the solvent removed in vacuo (in the case of run 9 the product was trapped at liquid nitrogen temperature), then deuterated benzene or chloroform was added and the composition and composition of material was checked by GC-MS and multinuclear NMR spectroscopy [7,11,14,15,16]. The products were separated by washing of 1 by pentane in the case of insoluble metal fluorides or by (vacuo) distillation in the case of fluorosilanes and fluorophosphine.…”