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从分离的 (III) 复合物中进行碳-碳键形成的减少消除

James R Bour¹, Nicole M Camasso¹, Elizabeth A Meucci¹

¹Department of Chemistry, University of Michigan , 930 N. University Avenue, Ann Arbor, Michigan 48109, United States.

Journal of the American Chemical Society

|December 15, 2016

概括

新的有机金属复合体显示出独特的反应性. 这些三酸三酸化合物在加热时形成新的碳-碳键,提供新的合成途径.

科学领域:

有机金属化学
催化剂
合成化学

背景情况:

复合物是有机合成中的多功能催化剂.
探索的较高氧化状态,如Ni (III),可以释放独特的反应性.
三酸 (Tp) 连接物为金属复合物提供稳定性和可调节的电子特性.

研究的目的:

设计,合成和描述新的有机金属Ni (III) 复合物.
研究这些Ni (III) 复合物的反应性和催化潜力.
探索由介导的新型C-C结合反应.

主要方法:

合成具有不同R和R1配体的酸复合物.
使用循环电压测量,EPR光谱和X射线晶体学进行表征.
涉及热激活诱导C-C键形成的反应性研究.

主要成果:

总结构TpNi (III) (R) (R1) 的稳定,室温可分离的Ni (III) 复合物已成功合成.
鉴定证实了Ni (III) 复合物的结构和电子特性.
在加热后,这些复合物促进了具有挑战性的C{\displaystyle C} -C{\displaystyle C} -C{\displaystyle C} -C{\displaystyle C} -C{\displaystyle C} -sp2键形成反应.

结论:

有机金属Ni(III) 复合物与tris(pyrazol) 酸连接物是稳定且可访问的.
这些Ni (III) 复合物具有独特的反应性,在温和的热条件下能够形成C-C键.
这项工作将介导催化剂的范围扩展到更高的氧化状态,提供新的合成方法.

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