Room Temperature Cyclopentadiene Elimination Reaction for the Synthesis of Diethylgallium−Amides, −Phosphides, and −Thiolates. Crystal and Molecular Structures of [Et2GaP(t-Bu)2]2 and [Et2GaS(SiPh3)]2

Autor:	Charles H. Lake, Melvyn Rowen Churchill, Laurence M. Toomey, Daniel B. Rosenblum, O. T. Beachley
Rok vydání:	1996
Předmět:	Cyclopentadiene Phosphide Organic Chemistry Inorganic chemistry Nuclear magnetic resonance spectroscopy Crystal structure Medicinal chemistry Inorganic Chemistry chemistry.chemical_compound Elimination reaction chemistry Yield (chemistry) Proton NMR Physical and Theoretical Chemistry Phosphine
Zdroj:	Organometallics. 15:3653-3658
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om960284p
Popis:	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.
Databáze:	OpenAIRE
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