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. 2019 Dec 19;4(27):22540-22548.
doi: 10.1021/acsomega.9b03251. eCollection 2019 Dec 31.

Facile Arene Ligand Exchange in p-Cymene Ruthenium(II) Complexes of Tertiary P-Chiral Ferrocenyl Phosphines

John Popp  1 , Schirin Hanf  1   2 , Evamarie Hey-Hawkins  1
Affiliations

Facile Arene Ligand Exchange in p-Cymene Ruthenium(II) Complexes of Tertiary P-Chiral Ferrocenyl Phosphines

John Popp et al. ACS Omega. .

Abstract

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.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Synthesis of P-Stereogenic Ferrocenyl Phosphine Boranes 1a,b
Figure 1
Figure 1
31P{1H} NMR spectra of the reaction of 2a with [{Ru(p-cym)Cl2}2] yielding monodentate complex 3a and, after light irradiation, chelate complex 4a.
Figure 2
Figure 2
Molecular structure of 4a in the solid state. Ellipsoids at 50% probability; hydrogen atoms are omitted for clarity.
Figure 3
Figure 3
Differences in the energy levels of the reaction of 2a to 3a and 4a calculated by DFT using the ORCA program package: BP86/def2-TZVP (see the Supporting Information for further details).
Figure 4
Figure 4
Molecular structure of 3b in the solid state. Ellipsoids at 50% probability, hydrogen atoms are omitted for clarity.
Figure 5
Figure 5
31P{1H} NMR spectra of the reaction of 2b with [{Ru(p-cym)Cl2}2], yielding the 1:1 complex 3b and, after several days at rt, formation of the 2:1 complex 4b by arene displacement.
Figure 6
Figure 6
Molecular structure of 4b in the solid state. Ellipsoids at 50% probability, hydrogen atoms are omitted for clarity.
Figure 7
Figure 7
Differences in the energy levels of the reaction of 2b to 3b and 4b calculated by DFT using the ORCA program package: BP86/def2-TZVP (see the Supporting Information for further details).
See this image and copyright information in PMC

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