Synthesis and Characterization of Anionic Halogen-Containing Rhodacarboranes. The Crystal and Molecular Structure of the Hydrogen Bonded Ion Pair, (HPPh3) (closo-3-(Ph3P)-3,3-(Br)2-3,1,2-RhC2B9H11).
Abstract
We recently reported the reaction of closo-3,3-(Ph3P)2-3-H-3,1,2-RhC2B9H11, 1, with benzoyl peroxide which afforded the asymmetric phosphinorhoadcarborane dimer (closo-(Ph3P)RhC2B9H11)2, 2, in modest yields (ca 40%).2 In order to conduct a more thorough study of the chemical reactivity and catalytic properties of this dimeric complex we sought a more efficient conversion of 1 to 2 employing Lewis acids. While the reactions of 1 with diborane and boron trifluoride did indeed proceed as that with boron tribromide produced a bromine-containing phosphinorhodacarborane in low yield which was shown by X-ray crystallography to be the ionic complex (HPPh3)(closo-3-(Ph3P)-3,3-(Br)2-3,1,2-RhC2B9H11), (HPPh3)3. Subsequent to the characterization of (HPPh3) 3 improved synthetic methods were developed which allowed the isolation of 3(-) with a variety of supporting counterions in good yields. Moreover, it was found that the iodo and chloro analogs of 3(-) could be easily prepared. Herein we report the details of these studies.
Document Details
- Document Type
- Technical Report
- Publication Date
- Mar 01, 1983
- Accession Number
- ADA128740
Entities
People
- Carolyn B. Knobler
- John A. Walker
- Limin Zheng
- M. Frederick Hawthorne
- R. Thomas Baker
Organizations
- University of California, Los Angeles