Different Reactivity of As4 towards Disilenes and Silylenes

Andreas E. Seitz; Maria Eckhardt; Sakya S. Sen; Andreas Erlebach; Eugenia V. Peresypkina; Herbert W. Roesky; Marek Sierka; Manfred Scheer

doi:10.1002/anie.201701740

Different Reactivity of As₄ towards Disilenes and Silylenes

Andreas E. Seitz, Maria Eckhardt, Sakya S. Sen, Andreas Erlebach, Eugenia V. Peresypkina, Herbert W. Roesky, Marek Sierka, Manfred Scheer

Лаборатория методов исследования состава и структуры функциональных материалов ФЕН

Результат исследования: Научные публикации в периодических изданиях › статья › рецензирование

9 Цитирования (Scopus)

Аннотация

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.

Язык оригинала	английский
Страницы (с-по)	6655-6659
Число страниц	5
Журнал	Angewandte Chemie - International Edition
Том	56
Номер выпуска	23
DOI	https://doi.org/10.1002/anie.201701740
Состояние	Опубликовано - 1 июн 2017

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10.1002/anie.201701740

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@article{5f32a9f6387e4f6baa3f1a8619d103e8,

title = "Different Reactivity of As4 towards Disilenes and Silylenes",

abstract = "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.",

keywords = "arsenic, density functional calculations, silicon, silylene, small-molecule activation, TRANSFORMATION, COMPLEXES, P-4 ACTIVATION, ELEMENTS, TETRAHEDRON, CAGE COMPOUNDS, DINITROGEN, WHITE PHOSPHORUS, BOND, AGGREGATION",

author = "Seitz, {Andreas E.} and Maria Eckhardt and Sen, {Sakya S.} and Andreas Erlebach and Peresypkina, {Eugenia V.} and Roesky, {Herbert W.} and Marek Sierka and Manfred Scheer",

year = "2017",

month = jun,

day = "1",

doi = "10.1002/anie.201701740",

language = "English",

volume = "56",

pages = "6655--6659",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "23",

}

Different Reactivity of As₄ towards Disilenes and Silylenes. / Seitz, Andreas E.; Eckhardt, Maria; Sen, Sakya S.; Erlebach, Andreas; Peresypkina, Eugenia V.; Roesky, Herbert W.; Sierka, Marek; Scheer, Manfred.

В: Angewandte Chemie - International Edition, Том 56, № 23, 01.06.2017, стр. 6655-6659.

Результат исследования: Научные публикации в периодических изданиях › статья › рецензирование

TY - JOUR

T1 - Different Reactivity of As4 towards Disilenes and Silylenes

AU - Seitz, Andreas E.

AU - Eckhardt, Maria

AU - Sen, Sakya S.

AU - Erlebach, Andreas

AU - Peresypkina, Eugenia V.

AU - Roesky, Herbert W.

AU - Sierka, Marek

AU - Scheer, Manfred

PY - 2017/6/1

Y1 - 2017/6/1

N2 - 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.

AB - 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.

KW - arsenic

KW - density functional calculations

KW - silicon

KW - silylene

KW - small-molecule activation

KW - TRANSFORMATION

KW - COMPLEXES

KW - P-4 ACTIVATION

KW - ELEMENTS

KW - TETRAHEDRON

KW - CAGE COMPOUNDS

KW - DINITROGEN

KW - WHITE PHOSPHORUS

KW - BOND

KW - AGGREGATION

UR - http://www.scopus.com/inward/record.url?scp=85018447524&partnerID=8YFLogxK

U2 - 10.1002/anie.201701740

DO - 10.1002/anie.201701740

M3 - Article

AN - SCOPUS:85018447524

VL - 56

SP - 6655

EP - 6659

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 23