Phosphenium-Insertion and Chloronium-Addition Reactions Involving the cyclo-Phosphanes (t-BuP)n (n = 3, 4)
Michael H. Holthausen A , Dane Knackstedt B C , Neil Burford B C D and Jan J. Weigand A D
+ Author Affiliations
- Author Affiliations
A Department of Chemistry and Food Chemistry, TU Dresden, Mommsenstr. 4, 01062 Dresden, Germany.
B Department of Chemistry, University of Victoria, PO Box 3065, Stn. CSC, Victoria, British Columbia, V8W 3V6, Canada.
C Department of Chemistry, Dalhousie University, Halifax, Nova Scotia B3H 4J3, Canada.
D Corresponding authors. Email: nburford@uvic.ca; jan.weigand@tu-dresden.de
Australian Journal of Chemistry 66(10) 1155-1162 https://doi.org/10.1071/CH13141
Submitted: 29 March 2013 Accepted: 7 May 2013 Published: 31 May 2013
Abstract
The transfer of a Ph2P+-moiety provided by Ph2PCl and chloronium-addition with PCl5 or PhICl2 to the cyclo-phosphanes (t-BuP)n (n = 3 (4), 4 (5)) were investigated. The reactions strongly depend on the presence of GaCl3 or Me3SiOTf as a halide abstracting reagent. The reaction of 4 with Ph2PCl and GaCl3 quantitatively yields cation [Ph2P(t-BuP)3]+ (6+) as a GaCl4–-salt. Using Me3SiOTf as a halide abstracting reagent leads to the ring expansion of (t-BuP)3 (4) to tetrameric (t-BuP)4 (5) and cation 6+ is only formed as a minor product. Chloronium addition employing the PCl5/GaCl3 or PhICl2/Me3SiOTf systems as Cl+-sources to 4 gives complex reaction mixtures. In contrast, the Cl+-addition to 5 gives cation [Cl(t-BuP)4]+ (8+) quantitatively when the system PCl5/GaCl3 is used. Utilising PhICl2 in the presence of Me3SiOTf gives t-BuPCl2 as the main product.
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