Autocatalytic degradation of white phosphorus with silylenes

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

Journal Article | Published | English

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Abstract
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.
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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.
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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7 Citations in Europe PMC

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