Reactivity of Phosphenium Ions toward 1,3- and 1,4-Dienes

A. H. Cowley, R. A. Kemp, J. G. Lasch, N. C. Norman, C. A. Stewart, B. R. Whittlesey, T. C. Wright

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41 Scopus citations

Abstract

The phosphenium ions [(i-Pr2N)2P]+ (1), [(Me2N)2P]+ (7), and [(i-Pr2N)ClP]+ (10) react with a variety of 1,3-dienes to afford the corresponding 3-phospholenium (1-phosphacyclopent-3-enium) cations. The product of the reaction of 1 with 2,3-dimethyl-1,3-butadiene (2) was characterized by X-ray crystallography. Compound 2 crystallizes in the space group P21/c (No. 14) with Z = 4, a = 9.005 (2) Å, b = 16.134 (4) Å, c = 18.271 (2) Å, and β = 96.94 (1)°. The product of the reaction of 7 with isoprene (11) was also characterized by X-ray crystallography. Compound 11 crystallizes in the monoclinic space group P21/c (No. 14) with a = 15.921 (2) Å, b = 7.903 (12) Å, c = 32.142 (4) Å, and β = 102.46 (1)°. The reactivity of 10 toward the 1,4-dienes, penta-1,4-diene and cyclohexa-1,4-diene, was also investigated. The product of the penta-1,4-diene reaction (15a) was characterized by X-ray crystallography. Compound 15a crystallizes in the orthorhombic space group P212121 (No. 19) with a = 8.309 (4) Å, b = 15.264 (2) Å, and c = 15.936 (2) Å. Mechanistic aspects of these reactions are discussed from the standpoint of product distribution.

Original languageEnglish
Pages (from-to)740-749
Number of pages10
JournalInorganic Chemistry
Volume25
Issue number6
DOIs
StatePublished - 1986

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