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Accessing Cationic α-Silylated and α-Germylated Phosphorus Ylides

Krämer, Felix; Radius, Michael; Hinz, Alexander ORCID iD icon; Dilanas, Melina E. A.; Breher, Frank


The synthesis and full characterization of α-silylated (α-SiCPs; 1–7) and α-germylated (α-GeCPs; 11–13) phosphorus ylides bearing one chloride substituent R$_{3}$PC(R$^{1}$)E(Cl)R$^{2}$$_{2}$ (R=Ph; R$^{1}$=Me, Et, Ph; R$^{2}$=Me, Et, iPr, Mes; E=Si, Ge) is presented. The molecular structures were determined by X-ray diffraction studies. The title compounds were applied in halide abstraction studies in order to access cationic species. The reaction of Ph$^{3}$PC(Me)Si(Cl)Me$^{2}$ (1) with Na[B(C$^{6}$F$^{5}$)$^{4}$] furnished the dimeric phosphonium-like dication [Ph$^{3}$PC(Me)SiMe$^{2}$]$^{2}$[B(C$^{6}$F$^{5}$)$^{4}$]$^{2}$ (8). The highly reactive, mesityl- or iPr-substituted cationic species [Ph$^{3}$PC(Me)SiMes$^{2}$][B(C$^{6}$F$^{5}$)$^{4}$] (9) and [Ph$^{3}$PC(Et)SiiPr$^{2}$][B(C$^{6}$F$^{5}$)$^{4}$] (10) could be characterized by NMR spectroscopy. Carrying out the halide abstraction reaction in the sterically demanding ether iPr$^{2}$O afforded the protonated α-SiCP [Ph$^{3}$PCH(Et)Si(Cl)iPr$^{2}$][B(C$^{6}$F$^{5}$)$^{4}$] (6 dec) by sodium-mediated basic ether decomposition, whereas successfully synthesized [Ph$^{3}$PC(Et)SiiPr$^{2}$][B(C$^{6}$F$^{5}$)$^{4}$] (10) readily cleaves the F−C bond in fluorobenzene. ... mehr

Verlagsausgabe §
DOI: 10.5445/IR/1000141487
Veröffentlicht am 27.12.2021
DOI: 10.1002/chem.202103974
Zitationen: 2
Web of Science
Zitationen: 2
Zitationen: 3
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Anorganische Chemie (AOC)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2021
Sprache Englisch
Identifikator ISSN: 0947-6539, 1521-3765
KITopen-ID: 1000141487
Erschienen in Chemistry - A European Journal
Verlag John Wiley and Sons
Band 28
Heft 1
Seiten e202103974
Nachgewiesen in Dimensions
Web of Science
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