TY - JOUR
T1 - Reactivity of Phosphenium Ions toward 1,3- and 1,4-Dienes
AU - Cowley, A. H.
AU - Kemp, R. A.
AU - Lasch, J. G.
AU - Norman, N. C.
AU - Stewart, C. A.
AU - Whittlesey, B. R.
AU - Wright, T. C.
PY - 1986
Y1 - 1986
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=0000062103&partnerID=8YFLogxK
U2 - 10.1021/ic00226a007
DO - 10.1021/ic00226a007
M3 - Article
AN - SCOPUS:0000062103
SN - 0020-1669
VL - 25
SP - 740
EP - 749
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 6
ER -