Synthese, Struktur und Eigenschaften des NatriumsilanidstBu2PhSiNa - ein Zugang zu Di-tert-butyl-phenylsilylsubstituierten Verbindungen

Abstract

Inhaltsu È bersicht. Das Natriumsilanid tBu 2 PhSiNa la È sst sich bei erho È hter Temperatur durch Einwirken von Na-Metall auf das Bromsilan tBu 2 PhSiBr in organischen Lo È sungsmitteln wie n-Heptan bzw. Ethern nahezu quantitativ gewinnen. Erstmals wurde mit tBu 2 PhSiNa ein Silanid, welches im Festko È rper ein kettenfo È rmiges Koordinationspolymer bildet, strukturell charakerisiert. Hierbei sind die tBu 2 PhSiNa-Einheiten durch g 6 Natrium±Phenyl-Kontakte miteinander verbru È ckt. Durch Oxidation mit Tetracyanethylen la È sst sich tBu 2 PhSiNa in das Disilan tBu 2 PhSi±SiPhtBu 2 u È berfu È hren.The Sodium Silanide tBu 2 PhSiNa: Synthesis, Properties, Structure Analysis ± a Synthetic Pathway to Introduce the tBu 2 PhSi-Ligand Abstract. The sodium silanide tBu 2 PhSiNa is easily obtained by the reaction of sodium metal with tBu 2 PhSiBr at elevated temperatures in n-heptane, THF or dibutylether. An X-ray crystal structure analysis reveals, that the sodium silanide 3 contains chains of tBu 2 PhSiNa units with g 6 sodium±phenyl-contacts. Oxidation of tBu 2 PhSiNa with TCNE proceeds with formation of the disilane tBu 2 PhSi±SiPhtBu 2 .

18F‐Labeling of Peptides by means of an Organosilicon‐Based Fluoride Acceptor

“…Syntheses of the organosilanes tBu 2 PhSiX (X = H, [20] F, [21] Cl, [20] I [21] ) and tBuPh 2 SiF [22] have been described elsewhere, however, different procedures were applied herein and all details are given in the Supporting Information, together with the synthetic procedures for p-(di-tert-butylfluorosilyl) benzaldehyde (5) and peptide 6. Noteworthy, in contrast to earlier reports tBu 2 PhSiF (4) was obtained as crystalline material and its molecular structure was determined by single-crystal X-ray diffraction.…”

Ditrielanes (R3Si)2E−E(SiR3)2 and Heterocubanes (R3Si)4E4Y4 (R3Si =tBu3Si,tBu2PhSi; E = Al, Ga, In, Tl; Y = O, Se)

“…The following compounds were synthesized according to literature procedures: NaR*, [33] NaR*·2THF, [33] NaRЈ, [3] R* 2 AlHal, [2] C 5 H 5 In, [34] C 5 Me 5 In, [35] TlN(SiMe 3 ) 2 , [36] C 5 H 5 Tl, [37] R* 4 Al 4 , [24] and R* 4 Ga 4 . The products R* 2 , [33] R*H, [33] R*Hal, [33] R*OH, [38] R*C 6 H 5 , [33] NaRЈ, [3] RЈ 2 , [39] RЈH, [39] RЈOH [39] were identified by comparison with authentic samples [tBu 3 29 Si NMR spectra were recorded with the INEPT or DEPT pulse sequence using empirically optimized parameters for the mentioned groups. After warming to 25°C, the light-yellow solution contained InN(SiMe 3 ) 2 exclusively according to the NMR spectra.…”

18F‐Markierung von Peptiden mithilfe eines Organosilicium‐Fluoridacceptors

“…Die Organosilane tBu 2 PhSiX (X = H, [20] F, [21] Cl, [20] I [21] ) und tBuPh 2 SiF [22] wurden in dieser Arbeit durch Methoden erhalten, die in den Hintergrundinformationen beschrieben sind. Weiterhin finden sich dort die Synthesevorschriften für p-(Di-tert-butylfluorsilyl)benzaldehyd (5) und das Peptid 6.…”