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.
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.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jun 24, 1996
- Accession Number
- ADA310565
Entities
People
- Charles H. Lake
- Daniel B. Rosenblum
- Laurence M. Toomey
- Melvyn Rowen M.R. Churchill
- O. T. Beachley Jr.
Organizations
- University at Buffalo