Accession Number : ADA310565
Title : Room Temperature Cyclopentadiene Elimination Reaction for the Synthesis of Diethylgallium-Amides, -Phosphides and -Thiolates, Crystal and Molecular Structures of Et2GaP(t-Bu)22 and Et2GaS(SiPh3)2.
Descriptive Note : Technical rept.,
Corporate Author : STATE UNIV OF NEW YORK AT BUFFALO DEPT OF CHEMISTRY
Personal Author(s) : Beachley, O. T., Jr. ; Rosenblum, Daniel B. ; Churchill, Melvyn R. ; Lake, Charles H. ; Toomey, Laurence M.
PDF Url : ADA310565
Report Date : 24 JUN 1996
Pagination or Media Count : 25
Abstract : The compounds Et2GaNEt22, Et2GaN(H)(Me)2, Et2GaN(H)(t-Bu)2, Et2GaP(i-Pr)22, Et2GaP(t-Bu)22, and Et2GaS(SiPh3)2 have been prepared in high yields at room temperature by the elimination of cyclopentadiene from Et2Ga(C5H5) and the corresponding amine, phosphine or thiol. The three diethylgallium amides and Et2GaP(i-Pr)22 are liquids whereas the other phosphide and the thiolate are crystalline solids at room temperature. All compounds were fully characterized by elemental analyses, (1)H and (31)P NMR spectroscopy and cryoscopic molecular weight studies in benzene, as appropriate and are dimeric in solution. The crystalline compounds Et2GaP(t-Bu)22 and Et2GaS(SiPh3)2 were characterized by X-ray structural studies. Even though Et2GaN(H)(t-Bu)2 and Et2GaS(SiPh3)2 were prepared at room temperature and isolated in high yield, (1)H NMR studies revealed that neither compound was formed in high yield in solution. Removal of the cyclopentadiene by either dimerization or distillation, and/or dimerization the gallium product are necessary to prevent the back reaction to reform the reactants.
Descriptors : *CRYSTAL STRUCTURE, *ROOM TEMPERATURE, *BUTYL RADICALS, *PHOSPHIDES, *MOLECULAR STRUCTURE, *AMIDES, *CYCLIC COMPOUNDS, *GALLIUM COMPOUNDS, *ETHYL RADICALS, *ELIMINATION REACTIONS, *PENTADIENES, REMOVAL, BENZENE, NUCLEAR MAGNETIC RESONANCE, SPECTROSCOPY, METHYL RADICALS, SYNTHESIS, STRUCTURAL PROPERTIES, MOLECULAR WEIGHT, CRYSTALS, SOLIDS, X RAYS, NITRIDES, SILICON, PHOSPHINE, PHENYL RADICALS, CRYOGENICS, DIMERS, DISTILLATION.
Subject Categories : Organic Chemistry
Atomic and Molecular Physics and Spectroscopy
Distribution Statement : APPROVED FOR PUBLIC RELEASE