The difference regarding the reactivity of the silanides Na[SitBu3] and Na[SiPhtBu2] towards white phosphorus

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2011
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Breitung, Sven
Sänger, Inge
Schödel, Frauke
Bolte, Michael
Lerner, Hans-Wolfram
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Inorganica Chimica Acta. 2011, 378(1), pp. 1-9. ISSN 0020-1693. eISSN 1873-3255. Available under: doi: 10.1016/j.ica.2011.07.050
Zusammenfassung

The sodium tetraphosphenediides Na2[tBu2RSiP–P=P–PSiRtBu2] (R = tBu, Ph) were formed when P4 was treated with two equivalents of the silanides Na[SiRtBu2] in thf. Whereas treatment of P4 with three equivalents of Na[SiPhtBu2] in thf gave the tetraphosphide Na3[P(PSiPhtBu2)3] as main product (along with, e.g., Na2[PSiPhtBu2], Na2[tBu2PhSiP–P=P–PSiPhtBu2], and Na2[P5(SiPhtBu2)3]). However, no tetraphosphide Na3[P(PSitBu3)3] was formed by the reaction of P4 with three equivalents of Na[SitBu3] in thf. The triphosphide Na[tBu2PhSiP–P=PSiPhtBu2] could be obtained together with Na[PHSiPhtBu2] by protolysis of Na3[P(PSiPhtBu2)3]. When a mixture of a 3:1 reaction of Na[SiPhtBu2] and P4 was heated to 100 °C in vacuo, {Na[P(SiPhtBu2)2]}2 was generated along with Na2[PSiPhtBu2] and P4. Single crystals of Na[P(SiPhtBu2)2] were grown from a heptane solution at room temperature (monoclinic space group C2/c).

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Fachgebiet (DDC)
540 Chemie
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White phosphorus; Silanides; X-ray structure analysis
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ISO 690LORBACH, Andreas, Sven BREITUNG, Inge SÄNGER, Frauke SCHÖDEL, Michael BOLTE, Matthias WAGNER, Hans-Wolfram LERNER, 2011. The difference regarding the reactivity of the silanides Na[SitBu3] and Na[SiPhtBu2] towards white phosphorus. In: Inorganica Chimica Acta. 2011, 378(1), pp. 1-9. ISSN 0020-1693. eISSN 1873-3255. Available under: doi: 10.1016/j.ica.2011.07.050
BibTex
@article{Lorbach2011-11diffe-39281,
  year={2011},
  doi={10.1016/j.ica.2011.07.050},
  title={The difference regarding the reactivity of the silanides Na[SitBu<sub>3</sub>] and Na[SiPhtBu<sub>2</sub>] towards white phosphorus},
  number={1},
  volume={378},
  issn={0020-1693},
  journal={Inorganica Chimica Acta},
  pages={1--9},
  author={Lorbach, Andreas and Breitung, Sven and Sänger, Inge and Schödel, Frauke and Bolte, Michael and Wagner, Matthias and Lerner, Hans-Wolfram}
}
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    <dcterms:abstract xml:lang="eng">The sodium tetraphosphenediides Na&lt;sub&gt;2&lt;/sub&gt;[tBu&lt;sub&gt;2&lt;/sub&gt;RSiP–P=P–PSiRtBu&lt;sub&gt;2&lt;/sub&gt;] (R = tBu, Ph) were formed when P&lt;sub&gt;4&lt;/sub&gt; was treated with two equivalents of the silanides Na[SiRtBu&lt;sub&gt;2&lt;/sub&gt;] in thf. Whereas treatment of P&lt;sub&gt;4&lt;/sub&gt; with three equivalents of Na[SiPhtBu&lt;sub&gt;2&lt;/sub&gt;] in thf gave the tetraphosphide Na&lt;sub&gt;3&lt;/sub&gt;[P(PSiPhtBu&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;3&lt;/sub&gt;] as main product (along with, e.g., Na&lt;sub&gt;2&lt;/sub&gt;[PSiPhtBu&lt;sub&gt;2&lt;/sub&gt;], Na&lt;sub&gt;2&lt;/sub&gt;[tBu&lt;sub&gt;2&lt;/sub&gt;PhSiP–P=P–PSiPhtBu&lt;sub&gt;2&lt;/sub&gt;], and Na&lt;sub&gt;2&lt;/sub&gt;[P&lt;sub&gt;5&lt;/sub&gt;(SiPhtBu&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;3&lt;/sub&gt;]). However, no tetraphosphide Na&lt;sub&gt;3&lt;/sub&gt;[P(PSitBu&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;3&lt;/sub&gt;] was formed by the reaction of P&lt;sub&gt;4&lt;/sub&gt; with three equivalents of Na[SitBu&lt;sub&gt;3&lt;/sub&gt;] in thf. The triphosphide Na[tBu&lt;sub&gt;2&lt;/sub&gt;PhSiP–P=PSiPhtBu&lt;sub&gt;2&lt;/sub&gt;] could be obtained together with Na[PHSiPhtBu&lt;sub&gt;2&lt;/sub&gt;] by protolysis of Na&lt;sub&gt;3&lt;/sub&gt;[P(PSiPhtBu&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;3&lt;/sub&gt;]. When a mixture of a 3:1 reaction of Na[SiPhtBu&lt;sub&gt;2&lt;/sub&gt;] and P4 was heated to 100 °C in vacuo, {Na[P(SiPhtBu2)2]}2 was generated along with Na2[PSiPhtBu2] and P&lt;sub&gt;4&lt;/sub&gt;. Single crystals of Na[P(SiPhtBu&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;] were grown from a heptane solution at room temperature (monoclinic space group C2/c).</dcterms:abstract>
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