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C–H Activation of Fluoroarenes: Synthesis, Structure, and Luminescence Properties of Copper(I) and Gold(I) Complexes Bearing 2-Phenylpyridine Ligands

Molteni, Roberto; Edkins, Katharina; Haehnel, Martin; Steffen, Andreas

C–H Activation of Fluoroarenes: Synthesis, Structure, and Luminescence Properties of Copper(I) and Gold(I) Complexes Bearing 2-Phenylpyridine Ligands Thumbnail


Authors

Roberto Molteni

Katharina Edkins

Martin Haehnel

Andreas Steffen



Abstract

Although 2-phenylpyridine (ppy)-type complexes have been employed very successfully for the design of luminescent IrIII and PtII complexes, corresponding d10-coinage metal complexes are unknown. We report on the synthesis of the first, room-temperature-stable, CuI ppy-type complexes, by C–H activation of 2-(2,3,4,5-tetrafluorophenyl)pyridine (Htfppy, 1) using [Cu(OH)(IDipp)] (2) (IDipp = bis(2,6-di-isopropylphenyl)imidazole-2-ylidene) or by lithiation of 1 and subsequent reaction with CuBr·SMe2 in the presence of a POP ligand (POP = bis{2-(diphenylphosphanyl)phenyl} ether) in THF, giving [Cu(tfppy)(IDipp)] (3) or [Cu(tfppy)(POP)] (4). The complexes thus obtained adopt distorted trigonal and tetrahedral coordination geometries, respectively. Gold(I) tfppy complexes with IDipp (5) or PTol3 (6) ligands have also been prepared, showing a preference for linear coordination environments due to the noncoordinating pyridine moiety of the tfppy ligand. These structural differences have a profound effect on the photophysical properties of the coinage metal ppy compounds. The CuI tfppy complexes exhibit intense orange-red luminescence (λmax = 610 (3), 607 (4) nm) from a 3(intraligand)CT state in the solid state at room temperature, with phosphorescence lifetimes of τ = 8.6 (3) and 9.5 (4) μs. In contrast, the linear coordination leads to weak emission of the AuI complexes, with 5 displaying simultaneous fluorescence and phosphorescence. Surprisingly, reaction of 2 with Htfppy (1) in MeCN leads to solvent activation and to isolation of a copper acetamide complex, [Cu(N(H)C(O)Me)(IDipp)] (14).

Citation

Molteni, R., Edkins, K., Haehnel, M., & Steffen, A. (2016). C–H Activation of Fluoroarenes: Synthesis, Structure, and Luminescence Properties of Copper(I) and Gold(I) Complexes Bearing 2-Phenylpyridine Ligands. Organometallics, 35(5), 629-640. https://doi.org/10.1021/acs.organomet.5b00904

Journal Article Type Article
Acceptance Date Mar 3, 2016
Online Publication Date Mar 3, 2016
Publication Date Mar 14, 2016
Deposit Date Mar 7, 2016
Publicly Available Date Mar 3, 2017
Journal Organometallics
Print ISSN 0276-7333
Electronic ISSN 1520-6041
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 35
Issue 5
Pages 629-640
DOI https://doi.org/10.1021/acs.organomet.5b00904
Public URL https://durham-repository.worktribe.com/output/1417720

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Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/acs.organomet.5b00904.




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