Silylierte Polyphenyläther; ihre Darstellung und einige physikalische Eigenschaften

Fink, William H.

doi:10.1002/hlca.19730560127

Cited by 7 publications

(1 citation statement)

References 3 publications

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“…Compound 1 was prepared by a modified literature procedure (Scheme ). , The dilithio reagent was prepared in THF at low temperature by metalation of diphenyl ether with 3 equiv of butyllithium followed by quenching with SiCl 4 and then reduction with lithium aluminum hydride to afford 1 as a viscous, pungent-smelling liquid in approximately 20% yield. The metalation of diphenyl ether in the presence of TMEDA has also been reported; however, attempts to prepare 1 using activation by TMEDA failed. When the dilithio reagent was quenched with Si(OMe) 4 instead of SiCl 4 before reduction with LiAlH 4 , formation of 1 was not observed.…”

Section: Resultsmentioning

confidence: 99%

Si−H Bond Activation by (Ph₃P)₂Pt(η²-C₂H₄) in Dihydrosilicon Tricycles that Also Contain O and N Heteroatoms

et al. 2006

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Several tricyclic phenoxasilin and phenazasiline heterocycles were synthesized from the corresponding 2,2‘-dilithio-diphenyl ether or diphenyl amine precursor and silicon tetrachloride (or trichlorosilane) followed by reduction with lithium aluminum hydride [H2SiAr2: Ar2 = C12H8O (1); Ar2 = C14H12O (2); Ar2 = C13H11N (3); Ar2 = C15H15N (4); Ar2 = C13H9Br2N (5)]. The reactivity of hydrosilanes 1−5 with (Ph3P)2Pt(η2-C2H4) (6) was investigated. At room temperature, mononuclear complexes, (Ph3P)2Pt(H)(SiAr2H) and (Ph3P)2Pt(SiAr2H)2, were generally observed by NMR spectroscopy but were too reactive or unstable to isolate. Dinuclear and in some cases trinuclear Pt−Si-containing complexes were observed as the major products from the reactions. Symmetrical dinuclear complexes, [(Ph3P)Pt(μ-η2-H-SiAr2)]2 (8 and 22, respectively), were produced from the reaction of 1 or 3 with 6. In contrast, reaction of silane 2 with 6 produced a trinuclear complex, [(Ph3P)Pt(μ-SiAr2)]3 (16), as the major product. However, reaction of 4 or 5 with complex 6 produced an unsymmetrical dinuclear complex, [(Ph3P)2Pt(H)(μ-SiAr2)(μ-η2-H-SiAr2)Pt(PPh3)] (26 and 30, respectively), as the major component. The molecular structures of a symmetrical (22) and unsymmetrical dinuclear (30) complex as well as a trinuclear (16) complex were determined by X-ray crystallography.

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Section: Resultsmentioning

confidence: 99%

Si−H Bond Activation by (Ph₃P)₂Pt(η²-C₂H₄) in Dihydrosilicon Tricycles that Also Contain O and N Heteroatoms

et al. 2006

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Zum Mechanismus basekatalysierter Carbodesilylierungen von Aryl‐ und Heteroaryltrimethylsilanen

Effenberger

Spiegler

1985

Chem. Ber.

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Die Einfliisse verschiedener Basen auf die Spaltung von Silicium-Kohlenstoff-Bindungen in Aryl-und Heteroaryltrimethylsilanen unter Bildung von Aryl-bzw. Heteroaryl-Anionen in Gegenwart von Benzaldehyd als Abfangelektrophil werden untersucht. Aus den Umsetzungen mit 2-(Trimethylsilyl)benzothiazol(l) wird eine Reaktivitatsreihenfolge der verwendeten basischen Katalysatoren ermittelt. Die katalytische Aktivitat der Anionen nimmt mit ihrem Ionenpotential zu. Als erster Reaktionsschritt wird der Angriff der Base am Si-Atom unter Ausbildung einer pentakoordinierten Zwischenstufe postuliert, die im geschwindigkeitsbestimmenden Schritt unter Bildung des Carbanions dissoziiert, das rasch mit dem Benzaldehyd reagiert. Die Abhangigkeit der basisch katalysierten Carbodesilylierung von der ArylAnionen-Stabilitat wird an unterschiedlich substituierten Aryltrimethylsilanen 13, 1 3 und 1 3 ' untersucht. Die ermittelten Reaktionsgeschwindigkeiten korrelieren besser rnit denHammettschen o-Werten als mit den Aryl-Anionen-Stabilitaten. Mechanism of Base-Catalyzed Desilylations of Aryl-and Heteroaryltrimethylsilanes')The influence of different bases on the cleavage of silicium-carbon bonds in aryl-and heteroaryltrimethylsilanes is investigated in the presence of benzaldehyde as electrophilic scavenger for the aryl and heteroaryl anions formed in this process. A reactivity gradation of the various basic catalysts employed is determined from the reactions with 2-(trimethylsilyl)-bcnzothiazole (1). The increase of catalytic activity of the anions parallels that of their ion potential. Attack of the base at the Si atom is postulated as the first step in this reaction sequence, with subsequent dissociation of the pentacoordinated intermediate in the ratedetermining step. The carbanion thus liberated rapidly reacts with benzaldehyde. In the differently substituted aryltrimethylsilanes 13, 13, and 13' the dependency of aryl anion stability in the base-catalyzed carbodesilylation was investigated. The relative rates of reaction correlate with Hammett's o-constants rather than with the corresponding aryl anion stabilities.

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ChemInform Abstract: SILYLIERTE POLYPHENYLAETHER, IHRE DARST. UND EINIGE PHYSIKALISCHE EIGENSCHAFTEN

Fink¹

1973

Chemischer Informationsdienst

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Silylierte Polyphenyläther; ihre Darstellung und einige physikalische Eigenschaften

Cited by 7 publications

References 3 publications

Si−H Bond Activation by (Ph₃P)₂Pt(η²-C₂H₄) in Dihydrosilicon Tricycles that Also Contain O and N Heteroatoms

Si−H Bond Activation by (Ph₃P)₂Pt(η²-C₂H₄) in Dihydrosilicon Tricycles that Also Contain O and N Heteroatoms

Zum Mechanismus basekatalysierter Carbodesilylierungen von Aryl‐ und Heteroaryltrimethylsilanen

ChemInform Abstract: SILYLIERTE POLYPHENYLAETHER, IHRE DARST. UND EINIGE PHYSIKALISCHE EIGENSCHAFTEN

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Silylierte Polyphenyläther; ihre Darstellung und einige physikalische Eigenschaften

Cited by 7 publications

References 3 publications

Si−H Bond Activation by (Ph3P)2Pt(η2-C2H4) in Dihydrosilicon Tricycles that Also Contain O and N Heteroatoms

Si−H Bond Activation by (Ph3P)2Pt(η2-C2H4) in Dihydrosilicon Tricycles that Also Contain O and N Heteroatoms

Zum Mechanismus basekatalysierter Carbodesilylierungen von Aryl‐ und Heteroaryltrimethylsilanen

ChemInform Abstract: SILYLIERTE POLYPHENYLAETHER, IHRE DARST. UND EINIGE PHYSIKALISCHE EIGENSCHAFTEN

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Si−H Bond Activation by (Ph₃P)₂Pt(η²-C₂H₄) in Dihydrosilicon Tricycles that Also Contain O and N Heteroatoms

Si−H Bond Activation by (Ph₃P)₂Pt(η²-C₂H₄) in Dihydrosilicon Tricycles that Also Contain O and N Heteroatoms