Autocatalytic degradation of white phosphorus with silylenes

Schoeller W (2009)
PHYSICAL CHEMISTRY CHEMICAL PHYSICS 11(26): 5273-5280.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Abstract / Bemerkung
White phosphorus (P-4) is prone to undergo degradation by nucleophiles and is reluctant to do so with electrophiles. Silylenes possess a strong singlet character but at the same time bear a largely inert lone pair orbital at the silicon atom. Thus they predominantly react in a similar way to electrophilic carbenes. Due to the poor pi-character of the P-P bonds in white phosphorus, the overlap with the empty orbital for the electrophilic silylene is less facile and results in a relatively large barrier for the addition reaction. The electrophilic approach of the silylene to white phosphorus is catalyzed by addition of a second P-4, forming a trigonal bipyramidal transition state geometry. Its stability towards fragmentation is essentially lower than that of the silyl cation. The entropy contributions for bimolecular versus termolecular reactions are discussed.
Erscheinungsjahr
2009
Zeitschriftentitel
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Band
11
Ausgabe
26
Seite(n)
5273-5280
ISSN
1463-9076
eISSN
1463-9084
Page URI
https://pub.uni-bielefeld.de/record/1633281

Zitieren

Schoeller W. Autocatalytic degradation of white phosphorus with silylenes. PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 2009;11(26):5273-5280.
Schoeller, W. (2009). Autocatalytic degradation of white phosphorus with silylenes. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 11(26), 5273-5280. doi:10.1039/b818396a
Schoeller, W. (2009). Autocatalytic degradation of white phosphorus with silylenes. PHYSICAL CHEMISTRY CHEMICAL PHYSICS 11, 5273-5280.
Schoeller, W., 2009. Autocatalytic degradation of white phosphorus with silylenes. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 11(26), p 5273-5280.
W. Schoeller, “Autocatalytic degradation of white phosphorus with silylenes”, PHYSICAL CHEMISTRY CHEMICAL PHYSICS, vol. 11, 2009, pp. 5273-5280.
Schoeller, W.: Autocatalytic degradation of white phosphorus with silylenes. PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 11, 5273-5280 (2009).
Schoeller, Wolfgang. “Autocatalytic degradation of white phosphorus with silylenes”. PHYSICAL CHEMISTRY CHEMICAL PHYSICS 11.26 (2009): 5273-5280.

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