Popp John, Hanf Schirin, Hey-Hawkins Evamarie
Faculty of Chemistry and Mineralogy, Institute of Inorganic Chemistry, Leipzig University, Johannisallee 29, 04103 Leipzig, Germany.
Department of Chemistry, Cambridge University, Lensfield Road, CB2 1EW Cambridge, U.K.
ACS Omega. 2019 Dec 19;4(27):22540-22548. doi: 10.1021/acsomega.9b03251. eCollection 2019 Dec 31.
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 -stereogenic ferrocenyl phosphines. By mild photochemical activation, the displacement of -cymene and subsequent tethering by η-coordination of the terminal phenyl ring of a biphenylyl-substituted ferrocenyl phosphine were enabled. Furthermore, the spontaneous -cymene displacement in a 2-methoxyphenyl-containing ferrocenyl phosphine and ensuing coordination of the ligand as a , 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.
半三明治型芳烃金属配合物通常用于特定应用。在此，我们报道了两种叔立体异构二茂铁基膦钌（II）配合物的芳烃配体交换反应。通过温和的光化学活化，实现了对异丙苯的取代以及联苯基取代的二茂铁基膦末端苯环通过η配位的连接。此外，还研究了含2-甲氧基苯基的二茂铁基膦中异丙苯的自发取代以及随后配体作为螯合物的配位情况。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。本文报道的可控芳烃取代的简便性可为新型定制催化剂的合成和设计提供新途径。
