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Facile Arene Ligand Exchange in p-Cymene Ruthenium(II) Complexes of Tertiary P-Chiral Ferrocenyl Phosphines.
ACS Omega ( IF 3.7 ) Pub Date : 2019-12-19 , DOI: 10.1021/acsomega.9b03251
John Popp 1 , Schirin Hanf 1, 2 , Evamarie Hey-Hawkins 1
Affiliation  

Half-sandwich arene-metal complexes are commonly used for specific applications. Herein, we report facile arene ligand exchange reactions of two ruthenium(II) complexes of tertiary P-stereogenic ferrocenyl phosphines. By mild photochemical activation, the displacement of p-cymene and subsequent tethering by η6-coordination of the terminal phenyl ring of a biphenylyl-substituted ferrocenyl phosphine were enabled. Furthermore, the spontaneous p-cymene displacement in a 2-methoxyphenyl-containing ferrocenyl phosphine and ensuing coordination of the ligand as a P,O chelate were examined. For both reactions, theoretical calculations of the general course of the reaction confirmed the experimental findings. The ease of the controlled arene displacement reported here can offer new pathways for the synthesis and design of novel tailor-made catalysts.

中文翻译:

叔对-手性二茂铁基膦的对异丙苯钌(II)配合物中的易芳烃配体交换。

半三明治芳烃金属配合物通常用于特定应用。在这里,我们报告了叔P-立体异构二茂铁基二膦的两个钌(II)配合物的容易的芳烃配体交换反应。通过温和的光化学活化,能够实现对苯异丙基的取代和随后通过联苯基取代的二茂铁基膦的末端苯基环的η6-配位进行束缚。此外,检查了在含2-甲氧基苯基的二茂铁基膦中的自发对-甲基异丙基苯的取代以及作为P,O螯合物的配体的配位作用。对于这两个反应,反应一般过程的理论计算证实了实验结果。本文报道的易于控制的芳烃置换可以为合成和设计新型量身定制的催化剂提供新的途径。
更新日期:2019-12-31
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