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Organophosphorus Compounds, Part 146* Imidovanadium(V) Complexes as Reaction Partners for Kinetically Stabilized Phosphaalkynes. Synthesis and Reactivity of 3-Aza-l,2,4,6-tetraphospha-quadricyclanes
-
Christoph Peters
and
Manfred Regitz
Published/Copyright:
June 2, 2014
The Lewis base adducts of imidovanadium(V) compounds 5a,b undergo chemoselective cyclooligomerization reactions with the kinetically stabilized phosphaalkynes 4a-e to furnish the azatetraphosphaquadricyclanes 6a-f with incorporation of the imido fragment. The reactivity of this novel class of heteropolycyclic compounds has been examined exemplarily for compound 6a. Complexation of one and two phosphorus atoms was achieved by reaction with nonacarbonyldiiron or the tungsten pentacarbonyl-THF complex resulting in the formation of the transition metal compounds 17-20. Reactions of 6a with the sulfonyl azides 21ac furnished the Staudinger products 22a-c. The reaction of 6a with two equivalents of tosyl azide gave a surprising result. No double complexation leading to a symmetrical product was achieved, and compound 23 was obtained instead in which the two phosphorus atoms of one diphosphirane ring are functionalized. Oxidative cleavage of a P/P bond in 6a to furnish product 24 is observed in the reaction of 6a with the Lewis base-free imidovanadium(V) species 15a.
Keywords: Cyclooligomerization of Phosphaalkynes; Imidovanadium(V) Complexes; 3-Aza-l,2,4,6-tetraphospha-quadricyclanes
Received: 2001-4-11
Published Online: 2014-6-2
Published in Print: 2001-9-1
© 1946 – 2014: Verlag der Zeitschrift für Naturforschung
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Keywords for this article
Cyclooligomerization of Phosphaalkynes;
Imidovanadium(V) Complexes;
3-Aza-l,2,4,6-tetraphospha-quadricyclanes
Articles in the same Issue
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