Control of cerium oxidation state through metal complex secondary structures
| Autor: | Jessica R. Levin, Walter L. Dorfner, Patrick J. Carroll, Eric J. Schelter |
|---|---|
| Rok vydání: | 2015 |
| Předmět: |
Coordination sphere
010405 organic chemistry Inorganic chemistry chemistry.chemical_element General Chemistry 010402 general chemistry Alkali metal Electrochemistry 01 natural sciences Magnetic susceptibility 0104 chemical sciences Metal Chemistry chemistry.chemical_compound Cerium Aniline chemistry Oxidation state visual_art visual_art.visual_art_medium |
| Zdroj: | Chemical Science |
| ISSN: | 2041-6539 2041-6520 |
| DOI: | 10.1039/c5sc02607e |
| Popis: | A series of alkali metal cerium diphenylhydrazido complexes, Mx(py)y[Ce(PhNNPh)4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. A series of alkali metal cerium diphenylhydrazido complexes, Mx(py)y[Ce(PhNNPh)4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li+ or Na+, the cerium(iii) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline. Reduction of 1,2-diphenylhydrazine was not observed when M = K+, and the complex remained in the cerium(iii) oxidation state. Oxidation of the cerium(iii) diphenylhydrazido complex to the Ce(iv) diphenylhydrazido one was achieved through a simple cation exchange reaction of the alkali metals. UV-Vis spectroscopy, FTIR spectroscopy, electrochemistry, magnetic susceptibility, and DFT studies were used to probe the oxidation state and the electronic changes that occurred at the metal centre. |
| Databáze: | OpenAIRE |
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