氧原子插入金属碳键的可变途径:Cp*W(O) 2(CH2SiMe3) 的情况
Jiajun Mei1, Kurtis M Carsch, Cody R Freitag
1Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904-4319, United States.
Journal of the American Chemical Society
|December 25, 2012
概括
有机金属复合物Cp * W ((O) ((2) ((CH ((2) SiMe ((3)) 与氧气供体发生反应,形成三甲基基甲醇. 观察到不同的反应途径与周期性和过氧化,涉及连接体迁移和质子分解.
科学领域:
- 有机金属化学 有机金属化学
- 的化学化学 的化学
- 氧化反应 氧化反应
背景情况:
- Cp*W{O}{2}{CH}{2}SiMe{3}) 是一个明确的有机金属复合体.
- 在催化和合成中,了解金属基键与氧气供体的反应性至关重要.
- 之前的研究已经探索了相关的复合物,但不同氧原子捐赠者的具体机制需要进一步阐明.
研究的目的:
- 研究Cp*W(O)(2)(CH(2)SiMe(3)) 与各种氧原子供体,特别是周期酸盐和过氧化的反应途径.
- 阐明三甲基基甲醇形成的机械细节.
- 为了比较不同氧源的反应性和机械性结果.
主要方法:
- 在THF/水中,Cp*W{O}{2}{CH}{2}SiMe{3}与IO{4}{-}和H{2}{O}{2}的反应.
- 反应中间体和产品的表征.
- 涉及酸催化物的机制研究.
主要成果:
- 与IO () 的反应通过IO () 的协调,连接物迁移和解离产生TMSCH () OH.
- 与H(2) O(2) 的反应形成一个2 - 氧复合体,Cp*W(O) 2 - O(2)) CH(2) SiMe(3)).
- 酸或催化转化乙2 - 氧复合物到TMSCH2OH通过不同的机械途径,涉及连接体迁移和质子分解.
结论:
- Cp*W(O)(2)(CH(2)SiMe(3)) 与氧原子捐赠体的反应通过不同的途径形成三甲基基甲醇.
- 氧气供体的性质决定了最初的反应路径,即直接的连接物迁移或过氧中间体的形成.
- 酸和两种催化都可以通过连接物迁移促进过氧中间体转化为最终的酒精产品.
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