Room Temperature Cyclopentadiene Elimination Reaction for the Synthesis of Diethylgallium-Amides, -Phosphides, and -Thiolates. Crystal and Molecular Structures of [Et2GaP(t-Bu)2]
详细信息 查看全文
- 作者：O. T. Beachley Jr. ; Daniel B. Rosenblum ; Melvyn Rowen Churchill ; Charles H. Lake ; and Laurence M. Toomey
- 刊名：Organometallics
- 出版年：1996
- 出版时间：August 20, 1996
- 年：1996
- 卷：15
- 期：17
- 页码：3653 - 3658
- 全文大小：162K
- 年卷期：v.15,no.17(August 20, 1996)
- ISSN：1520-6041
文摘
The compounds[Et2GaNEt2]2,[Et2GaN(H)(Me)]2,[Et2GaN(H)(t-Bu)]2,[Et2GaP(i-Pr)2]2,[Et2GaP(t-Bu)2]2, and[Et2GaS(SiPh3)]2 havebeen prepared in high yields at room temperatureby the elimination of cyclopentadiene fromEt2Ga(C5H5) and thecorresponding amine,phosphine, or thiol. The three diethylgallium amides and[Et2GaP(i-Pr)2]2 areliquids,whereas the other phosphide and the thiolate are crystalline solids atroom temperature.All compounds were fully characterized by elemental analyses,1H and 31P NMR spectroscopy,and cryoscopic molecular weight studies in benzene, as appropriate, andare dimeric insolution. The crystalline compounds[Et2GaP(t-Bu)2]2, and[Et2GaS(SiPh3)]2 werecharacterized by X-ray structural studies. Even though[Et2GaN(H)(t-Bu)]2 and[Et2GaS(SiPh3)]2wereprepared at room temperature and isolated in high yield, 1HNMR studies revealed thatneither compound was formed in high yield in solution. Removal ofthe cyclopentadiene byeither dimerization or distillation and/or dimerization of the galliumproduct are necessaryto prevent the back-reaction to re-form the reactants.