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Chemoselective Preparation of 1-Iodoalkynes, 1,2-Diiodoalkenes, and 1,1,2-Triiodoalkenes Based on the Oxidative Iodination of Terminal Alkynes
Published on: September 12, 2018
Structural diversity in a series of alkyl-substituted cesium aryloxides
Timothy J Boyle1, Leigh Anna M Steele, Alia M Saad
1Advanced Materials Laboratory, Sandia National Laboratories, 1001 University Boulevard SE, Albuquerque, New Mexico 87106, USA. tjboyle@Sandia.gov
Abstract:
A family of cesium aryloxides [Cs(OAr)](n) were synthesized and structurally characterized from the reaction of 1:1 or 1:excess stoichiometry of Cs(0) and the appropriate alkyl-substituted phenol: 2-alkylphenol [alkyl = methyl (H-oMP), isopropyl (H-oPP), and tert-butyl (H-oBP)] and 2,6-dialkylphenol [alkyl = methyl (H-DMP), isopropyl (H-DIP), tert-butyl (H-DBP), and phenyl (H-DPhP)]. The products were structurally identified as [Cs(oMP)(H-oMP)(2)](n) (1), [Cs(5)(oPP)(5)](n) (2), [Cs(4)(oBP)(4)(H-oBP)(6)](n) (3x, shown), [Cs(3)(DMP)(3)](n) (4), [Cs(2)(DIP)(2)](n) (5), [Cs(DIP)(H-DIP)](n) (5x), and [Cs(DPhP)](n) (7). Compounds 1-7 were found to adopt complex polymeric structures employing π interactions from the neighboring pendant phenoxide ligands. The solution behavior of these compounds was studied using solution (133)Cs NMR spectroscopy, and for each compound, a single (133)Cs NMR resonance was observed, with chemical shift values found to be strongly solvent-dependent. This implies that monomeric cesium salt species involving solvent interactions exist in solution.
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