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4,5-Diazafluorene and 9,9’-Dimethyl-4,5-Diazafluorene as Ligands Supporting Redox-Active Mn and Ru Complexes
Henke, Wade C. Hopkins, Julie A. Anderson, Micah L. Stiel, Jonah P. Day, Victor W. Blakemore, James D.
Henke, Wade C.
Hopkins, Julie A.
Anderson, Micah L.
Stiel, Jonah P.
Day, Victor W.
Blakemore, James D.
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Abstract
4,5-diazafluorene (daf) and 9,9’-dimethyl-4,5-diazafluorene (Me2daf) are structurally similar to the important ligand 2,2’-bipyridine (bpy), but significantly less is known about the redox and spectroscopic properties of metal complexes containing Me2daf as a ligand than those containing bpy. New complexes Mn(CO)3Br(daf) (2), Mn(CO)3Br(Me2daf) (3), and [Ru(Me2daf)3](PF6)2 (5) have been prepared and fully characterized to understand the influence of the Me2daf framework on their chemical and electrochemical properties. Structural data for 2, 3, and 5 from single-crystal X-ray diffraction analysis reveal a distinctive widening of the daf and Me2daf chelate angles in comparison to the analogous Mn(CO)3(bpy)Br (1) and [Ru(bpy)3]2+ (4) complexes. Electronic absorption data for these complexes confirm the electronic similarity of daf, Me2daf, and bpy, as spectra are dominated in each case by metal-to-ligand charge transfer bands in the visible region. However, the electrochemical properties of 2, 3, and 5 reveal that the redox-active Me2daf framework in 3 and 5 undergoes reduction at a slightly more negative potential than that of bpy in 1 and 4. Taken together, the results indicate that Me2daf could be useful for preparation of a variety of new redox-active compounds, as it retains the useful redox-active nature of bpy but lacks the acidic, benzylic C–H bonds that can induce secondary reactivity in complexes bearing daf.
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This work is licensed under a Creative Commons Attribution 4.0 International License.
Date
2020-07-13
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MDPI
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Keywords
Manganese tricarbonyl, Ruthenium, Electrochemistry, 4,5-diazafluorene, 9,9’-dimethyl-4,5-diazafluorene
Citation
Henke, W. C., Hopkins, J. A., Anderson, M. L., Stiel, J. P., Day, V. W., & Blakemore, J. D. (2020). 4,5-Diazafluorene and 9,9'-Dimethyl-4,5-Diazafluorene as Ligands Supporting Redox-Active Mn and Ru Complexes. Molecules (Basel, Switzerland), 25(14), 3189. https://doi.org/10.3390/molecules25143189