精细调整金属介导二二NN键裂变的能量屏障
Andrew J Keane1, Brendan L Yonke, Masakazu Hirotsu
1Department of Chemistry and Biochemistry, University of Maryland , College Park, Maryland 20742, United States.
Journal of the American Chemical Society
|June 25, 2014
概括
这项研究揭示了二金属二化合物中-键裂变是如何发生的. 在R替代剂中的立体和电子因素控制反应速率,影响动力稳定性.
科学领域:
- 有机金属化学 有机金属化学
- 无机化学 无机化学
- 固定的研究 固的研究
背景情况:
- 二化合物是固化的关键中间体.
- 了解NN键裂解机制是开发高效催化剂的关键.
- 第5组双金属复合物提供了一个研究NN键激活的平台.
研究的目的:
- 阐明5组双金属二氧化复合体中NN键裂解的机制.
- 研究替代剂的固体和电子性质对NN键裂解动学的影响.
- 为了合理化第一排同源的不同稳定性.
主要方法:
- 合成和表征双金属二化合物复合物 {Cp*M[N((i) Pr) C(R) N((i) Pr) ]}2(μ-N2).
- 溶液相运动研究以确定激活参数.
- 计算分析以了解电子结构和结合.
主要成果:
- 支持了一种涉及从端上桥梁到侧上桥梁二的分子内异构化机制.
- 实现了量化转换为双金属 bis ((μ-化物) 复合物 {Cp*M[N (((i) Pr) C (((R) N (((i) Pr) ]{μ-N) }2.
- 替代R的变化 (Me,Ph,NMe2) 调节了NN键裂屏障.
- 同源的较低稳定性归因于其电子结构.
结论:
- 这些复合体中的NN键裂变通过异构化驱动的途径进行.
- 替代效应为调反应性和动力稳定性提供了一个处理器.
- 电子结构决定了二联体对裂变的易感性.
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