Control of cerium oxidation state through metal complex secondary structuresElectronic supplementary information (ESI) available: NMR spectra, UV-Vis spectra, FTIR spectra, Evans' method data, field dependence data, XAS spectra, electrochemical data, DFT coordinates and rendered molecular orbitals. CCDC 1404761-1404763. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc02607e

A series of alkali metal cerium diphenylhydrazido complexes, M x (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 resulti...

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Main Authors: Levin, Jessica R, Dorfner, Walter L, Carroll, Patrick J, Schelter, Eric J
Format: Article
Language:English
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Summary:A series of alkali metal cerium diphenylhydrazido complexes, M x (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. A series of alkali metal cerium diphenylhydrazido complexes, M x (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.
ISSN:2041-6520
2041-6539
DOI:10.1039/c5sc02607e