5 years ago

Different Reactivity of As4 towards Disilenes and Silylenes

Different Reactivity of As4 towards Disilenes and Silylenes
Andreas E. Seitz, Marek Sierka, Maria Eckhardt, Eugenia V. Peresypkina, Herbert W. Roesky, Andreas Erlebach, Sakya S. Sen, Manfred Scheer
The activation of yellow arsenic is possible with the silylene [PhC(NtBu)2SiN(SiMe3)2] (1) and the disilene [(Me3Si)2N(η1-Me5C5)Si=Si(η1-Me5C5)N(SiMe3)2] (3). The reaction of As4 with 1 leads to the unprecedented As10 cage compound [(LSiN(SiMe3)2)3As10] (2; L=PhC(NtBu)2) with an As7 nortricyclane core stabilized by arsasilene moieties containing silicon(II)bis(trimethylsilyl)amide substituents. In contrast, the compound [Cp*{(SiMe3)2N}SiAs]2 (4) containing a butterfly-like diarsadisilabicyclo[1.1.0]butane unit is formed by the reaction of As4 with the disilene 3. Both compounds were characterized by single-crystal X-ray diffraction analysis, NMR spectroscopy, and mass spectrometry. The reaction outcomes demonstrate the different reaction behavior of yellow arsenic (As4) compared to white phosphorus (P4) in the reactions with the corresponding silylenes and disilenes. As revealed: The reaction of yellow arsenic with the silylene [PhC(NtBu)2SiN(SiMe3)2] and the disilene [(Me3Si)2N(η1-Me5C5)Si=Si(η1-Me5C5)N(SiMe3)2] gives an As10 cage compound with a nortricyclane core and a diarsadisila-butterfly derivative, respectively. These reactions demonstrate the different reaction behavior of yellow arsenic As4 and white phosphorus P4 with the corresponding silicon derivatives.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201701740

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