Synthesis and Characterization of Alkali-Metal Salts of 2,2′- and 2,4′-Bipyridyl Radicals and Dianions
- 12 August 2009
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 48 (17), 8304-8316
- https://doi.org/10.1021/ic9009459
Abstract
The reaction of ethylenediamine (en) solutions of 2,2′- and 2,4′-bipyridine (bipy) with varying stoichiometric amounts of potassium and rubidium metal resulted in the isolation of compositionally pure solids containing the respective bipyridyl radical anions (2,2′- and 2,4′-bipy•−) and dianions (2,2′- and 2,4′-bipy2−). These species were structurally characterized by single-crystal X-ray diffraction in K(2,2′-bipy)(en) (1a), K4(2,2′-bipy)4(en)4 (1b), Rb2(2,2′-bipy)(en)2 (2), K(2,4′-bipy)(en) (3), K4(2,4′-bipy)2(en)3.5 (4), and Rb4(2,4′-bipy)2(en)3.5 (5). The crystallographic results obtained allow for interesting relationships to be drawn between the electronic structure of the bipyridyl moieties and metric structural data. Further characterization of the solids by means of powder X-ray diffraction, elemental analysis, electron paramagnetic resonance, and IR and Raman spectroscopy is also reported. These studies provide a comprehensive overview of the structural and spectroscopic properties of these often-cited yet elusive air- and moisture-sensitive species, helping to complement the existing data in the chemical literature.Keywords
This publication has 59 references indexed in Scilit:
- Decamethylytterbocene Complexes of Bipyridines and Diazabutadienes: Multiconfigurational Ground States and Open-Shell Singlet FormationJournal of the American Chemical Society, 2009
- EasySpin, a comprehensive software package for spectral simulation and analysis in EPRJournal of Magnetic Resonance, 2006
- [20] Processing of X-ray diffraction data collected in oscillation modeMethods in Enzymology, 1997
- Reactivity of Decamethylsamarocene with Polycyclic Aromatic HydrocarbonsJournal of the American Chemical Society, 1994
- Resonance Raman study of the radical anion of 2,2′-bipyridine in a glassy matrix at 77 KJournal of Raman Spectroscopy, 1991
- Resonance Raman spectra and normal modes of vibration of 2,2′-bipyridine anion radicalsJournal of Raman Spectroscopy, 1990
- Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitalsThe Journal of Chemical Physics, 1985
- Bis(2,2'-bipyridyl)diisopropoxymolybdenum(II). Structural and spectroscopic evidence for molybdenum-to-bipyridyl .pi.* bondingJournal of the American Chemical Society, 1981
- Electronic spectra of tris(2,2′-bipyridyl) complexes—IJournal of Inorganic and Nuclear Chemistry, 1970
- Neutralkomplexe des 2,2′‐Dipyridyls Teil I Darstellung und EigenschaftenZeitschrift für Chemie, 1962