358-43-0Relevant articles and documents
Kruglaya et al.
, (1977)
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Flood
, p. 1735 (1933)
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Redox-state dependent activation of silanes and ammonia with reverse polarity (PCcarbeneP)Ni complexes: electrophilic vs. nucleophilic carbenes
LaPierre, Etienne A.,Piers, Warren E.,Gendy, Chris
, p. 16789 - 16797 (2018)
A rigidified PCalkylP ligand allowed for the synthesis and characterization of cationic and radical PCCarbeneP nickel complexes in which the carbene anchor of the pincer framework is electrophilic rather than nucleophilic. Alpha-hydride abstraction from a (PCalkylP)nickel halide complex readily leads to the cationic carbene complex, which furnishes the radical carbene complex by one electron reduction. The reactivity of these reverse polarity carbene complexes towards small molecules (H2, CO, CO2, R3SiH, NH3) reveals different modes of activation when compared to previously reported nucleophilic nickel carbene complexes, and a clear dependence on the redox state of the complex. For H2, CO and CO2, no reaction is observed, but silanes react via hydride transfer and formation of solvated silylium ions. Ammonia is activated in a novel way, wherein it coordinates the carbene carbon and is deprotonated to form a robust C-N bond. This is not only a rare example of ammonia activation by a first row transition metal but also evidence of the intermediacy of group 10 carbenes in direct C-N bond forming reactions.
Fernandez,M.J.,Bailey,P.M.,Bentz,P.O.
, p. 5458 (1984)
Synthesis of bis(trifluoromethyl)alkylated trisubstituted alkenes via highly regioselective catalyzed hydrosilylation reaction of hexafluoro-2-butyne and their reactivity
Filatov, Andrey A.,Jackson, Andrew,Kirij, Nataliia V.,Peng, Sheng,Yagupolskii, Yurii L.
, (2021/11/24)
Hydrosilylation reaction of hexafluoro-2-butyne 1 (HFB) with various silanes in the presence of a catalytic amount of transition-metal-catalysts was investigated. The reaction of HFB gave the corresponding bis(trifluoromethyl)containing vinylsilanes in an excellent regioselective manner in high yields. Treatment of the resulting vinylsilanes with various aldehydes and ketones in the presence of fluoride ion sources afforded the coupling products in moderate yields.
Bis(perfluoropinacolato)silane: A Neutral Silane Lewis Superacid Activates Si?F Bonds
Greb, Lutz,Hanusch, Franziska,Inoue, Shigeyoshi,Thorwart, Thadd?us,Tschernuth, Florian S.
supporting information, p. 25799 - 25803 (2021/11/09)
Despite the earth abundance and easy availability of silicon, only few examples of isolable neutral silicon centered Lewis superacids are precedent in the literature. To approach the general drawbacks of limited solubility and unselective deactivation pathways, we introduce a Lewis superacid, based on perfluorinated pinacol substituents. The compound is easily synthesized on a gram-scale as the corresponding acetonitrile mono-adduct 1?(MeCN) and was fully characterized, including single crystal X-ray diffraction analysis (SC-XRD) and state-of-the-art computations. Lewis acidity investigations by the Gutmann-Beckett method and fluoride abstraction experiments indicate a Lewis superacidic nature. The challenging Si?F bond activation of Et3SiF is realized and promising catalytic properties are demonstrated, consolidating the potential applicability of silicon centered Lewis acids in synthetic catalysis.
Isolable Silicon-Based Polycations with Lewis Superacidity
Hermannsdorfer, André,Driess, Matthias
supporting information, p. 23132 - 23136 (2020/10/19)
Molecular silicon polycations of the types R2Si2+ and RSi3+ (R=H, organic groups) are elusive Lewis superacids and currently unknown in the condensed phase. Here, we report the synthesis of a series of isolable terpyridine-stabilized R2Si2+ and RSi3+ complexes, [R2Si(terpy)]2+ (R=Ph 12+; R2=C12H8 22+, (CH2)3 32+) and [RSi(terpy)]3+ (R=Ph 43+, cyclohexyl 53+, m-xylyl 63+), in form of their triflate salts. The stabilization of the latter is achieved through higher coordination and to the expense of reduced fluoride-ion affinities, but a significant level of Lewis superacidity is nonetheless retained as verified by theory and experiment. The complexes activate C(sp3)?F bonds, as showcased by stoichiometric fluoride abstraction from 1-fluoroadamantane (AdF) and the catalytic hydrodefluorination of AdF. The formation of the crystalline adducts [2(F)]+ and [5(H)]2+ documents in particular the high reactivity towards fluoride and hydride donors.