了解d(0) -olefin转化催化剂:哪种金属,哪种连接体?
Albert Poater1, Xavier Solans-Monfort, Eric Clot
1Institut Charles Gerhardt, Université Montpellier 2, CNRS, Case Courier 1501, Place E Bataillon, Chimie Théorique, Méthodologies, Modélisations, Montpellier, France.
密度函数理论 (DFT) 的计算显示,非对称的氨酸转化催化剂的效率更高. (Mo) 和 (W) 催化剂的性能优于 (Re),除非Re被不对称地替换.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 计算化学计算化学
背景情况:
- 奥莱芬转化是有机合成和聚合物化学中的关键反应.
- 了解催化剂反应性是设计更高效的催化系统的关键.
- 模型系统用于阐明反应机制和电子效应.
研究的目的:
- 用密度函数理论 (DFT) 来研究乙烯与模型烯基转化催化剂的反应性.
- 为了比较基于 (Mo), (W) 和 (Re) 的催化剂的效率.
- 确定影响催化剂性能和反应途径的关键因素.
主要方法:
- 密度函数理论 (DFT) 的计算,特别是B3PW91的函数.
- 催化剂系统的建模M (NR) (CHCH3) (X) (Y),其中M=Mo,W;R=甲基,;X,Y=各种基,基或基组.
- 使用稳定状态近似计算反应能量概况和周转频率 (TOF).
主要成果:
- 一般的反应途径包括氨酸协调, [2+2] 循环添加,循环逆转和脱协调.
- 催化剂扭曲能量和金属循环稳定性 (M-C键强度) 显著影响能量概况.
- 不对称的催化剂 (X ≠ Y) 在所有金属系统 (Mo,W,Re) 中表现出系统性更高的效率 (TOF).
结论:
- 摩和W催化剂通常比Re催化剂更高效.
- 不对称的替换提高了催化剂的效率,使得即使是Re催化剂也具有竞争力.
- DFT计算提供了对氨酸转化催化剂设计和性能的宝贵见解.
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