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Title: Control of cerium oxidation state through metal complex secondary structures

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. As a result, 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.
Authors:
 [1] ;  [1] ;  [1] ;  [1]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
Publication Date:
Grant/Contract Number:
SC0006518
Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Research Org:
Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Orgs:
National Science Foundation (NSF), Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1221895

Levin, Jessica R., Dorfner, Walter L., Carroll, Patrick J., and Schelter, Eric J.. Control of cerium oxidation state through metal complex secondary structures. United States: N. p., Web. doi:10.1039/C5SC02607E.
Levin, Jessica R., Dorfner, Walter L., Carroll, Patrick J., & Schelter, Eric J.. Control of cerium oxidation state through metal complex secondary structures. United States. doi:10.1039/C5SC02607E.
Levin, Jessica R., Dorfner, Walter L., Carroll, Patrick J., and Schelter, Eric J.. 2015. "Control of cerium oxidation state through metal complex secondary structures". United States. doi:10.1039/C5SC02607E. https://www.osti.gov/servlets/purl/1221895.
@article{osti_1221895,
title = {Control of cerium oxidation state through metal complex secondary structures},
author = {Levin, Jessica R. and Dorfner, Walter L. and Carroll, Patrick J. and Schelter, Eric J.},
abstractNote = {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. As a result, 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.},
doi = {10.1039/C5SC02607E},
journal = {Chemical Science},
number = ,
volume = ,
place = {United States},
year = {2015},
month = {8}
}

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