ROOM-TEMPERATURE CYCLOPENTADIENE ELIMINATION-REACTION FOR THE SYNTHESIS OF DIETHYLGALLIUM-AMIDES, DIETHYLGALLIUM-PHOSPHIDES, AND DIETHYLGALLIUM-THIOLATES - CRYSTAL AND MOLECULAR-STRUCTURES OF [ET(2)GAP(T-BU)(2)](2) AND [ET(2)GAS(SIPH(3))](2)
Ot. Beachley et al., ROOM-TEMPERATURE CYCLOPENTADIENE ELIMINATION-REACTION FOR THE SYNTHESIS OF DIETHYLGALLIUM-AMIDES, DIETHYLGALLIUM-PHOSPHIDES, AND DIETHYLGALLIUM-THIOLATES - CRYSTAL AND MOLECULAR-STRUCTURES OF [ET(2)GAP(T-BU)(2)](2) AND [ET(2)GAS(SIPH(3))](2), Organometallics, 15(17), 1996, pp. 3653-3658
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)Ga
S(SiPh(3))](2) have been prepared in high yields at room temperature b
y the elimination of cyclopentadiene from Et(2)Ga(C5H5) and the corres
ponding amine, phosphine, or thiol. The three diethylgallium amides an
d [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 spec
troscopy, and cryoscopic molecular weight studies in benzene, as appro
priate, and are dimeric in solution. The crystalline compounds [Et(2)G
aP(t-Bu)(2)](2), and [Et(2)GaS(SiPh(3))](2) were characterized by X-ra
y 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 y
ield, H-1 NMR studies revealed that neither compound was formed. in hi
gh yield in solution. Removal of the cyclopentadiene by either dimeriz
ation or distillation and/or dimerization of the gallium product are n
ecessary to prevent the back-reaction to re-form the reactants.