在三坐标Ni(I) silyl复合物的氧化后,停止了从到的1,2-迁移
Vlad M Iluc1, Gregory L Hillhouse
1Gordon Center for Integrative Science, Department of Chemistry, University of Chicago, Chicago, Illinois 60637, USA.
Journal of the American Chemical Society
|August 10, 2010
概括
这项研究详细介绍了新型-复合物的合成. 观察到一个独特的三中心,两电子键在由 (II) 复合物形成的结果中,该复合物具有--相互作用.
科学领域:
- 有机金属化学 有机金属化学
- 无机化学 无机化学 有机化学
- 协调化学 协调化学
背景情况:
- 复合物与重的配体在催化过程中至关重要.
- 基联结物提供独特的反应性和结合模式.
- 了解Ni-Si相互作用是开发新催化系统的关键.
研究的目的:
- 合成和表征新的三坐标 () () 复合物.
- 研究这些复合物的反应性,特别是它们的氧化和迁移途径.
- 为了探索-化学中的不寻常的粘合图案.
主要方法:
- 通过对二元化物复合物与二元化物化物复合物的反应合成 (I) 复合物.
- 制备 (I) 复合物通过氧化添加三甲酸到 (O) 复合物.
- 使用铁氧化 (I) 复合物的单电子氧化产生 (II) 复合物.
- 使用光谱和分析技术对产生的复合体进行表征.
主要成果:
- 实现了三坐标Ni (I) 烯复合物的合成, (dtbpe) Ni (SiHMes) 2),实现了.
- 氧化添加Mes(2)Si(H) OTf到一个Ni(0) 复合物提供了对Ni(I) silyl复合物的替代途径.
- 一个电子的氧化产生了一个Ni(II) 复合体,[(dtbpe) Ni(mu-H) SiMes(2) ]][BAr(F) ((4),呈现出一个3中心,2电子的键.
- 复合物5也通过Mes(2) SiH(2) 激活由新复合盐而形成.
结论:
- 新型-复合物已经成功合成和表征.
- 发现了一种独特的3中心,2电子的结合相互作用,涉及,和.
- 该研究强调了-键形成和反应性的新途径.
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