Room temperature cyclopentadiene elimination reaction for the synthesis of diethylgallium-amides, -phosphides, and -thiolates. Crystal and molecular structures of [Et(2)GaP(t-Bu)(2)](2) and [Et(2)GaS(SiPh(3))](2)

The compounds [Et(2)GaNEt(2)](2), [Et(2)GaN(H)(Me)](2), [Et(2)GaN(H)(t-Bu)](2), [Et(2)GaP(i-Pr)(2)](2), [Et(2)GaP(t-Bu)(2)](2), and [Et(2)GaS(SiPh(3))](2) have been prepared in high yields at room temperature by the elimination of cyclopentadiene from Et(2)Ga(C5H5) and the corresponding amine, phosphine, or thiol. The three diethylgallium amides and [Et(2)GaP(i-Pr)(2)](2) are liquids, whereas the other phosphide and the thiolate are crystalline solids at room temperature, All compounds were fully characterized by elemental analyses, H-1 and P-31 NMR spectroscopy, and cryoscopic molecular weight studies in benzene, as appropriate, and are dimeric in solution. The crystalline compounds [Et(2)GaP(t-Bu)(2)](2), and [Et(2)GaS(SiPh(3))](2) were characterized by X-ray structural studies. Even though [Et(2)GaN(H)(t-Bu)](2) and [Et(2)GaS(SiPh(3))](2) were prepared at room temperature and isolated in high yield, H-1 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 of the gallium product are necessary to prevent the back-reaction to re-form the reactants.