Stable Open-Shell Phosphorane Based on a Redox-Active Amidodiphenoxide Scaffold
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Stable open-shell.pdf
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Author(s)
Pistner, Allen J.
Moon, Hye Won
Silakov, Alexey
Yennawar, Hemant P.
Radosevich, Alexander T.
Date Issued
August 2017
Journal
Inorganic Chemistry
Publisher
American Chemical Society (ACS)
Citation
Pistner, Allen J. et al. “Stable Open-Shell Phosphorane Based on a Redox-Active Amidodiphenoxide Scaffold.” Inorganic Chemistry 56, 15 (June 2017): 8661–8668 © 2017 American Chemical Society
Version
Author's final manuscript
Abstract
The synthesis and redox reactivity of pentacoordinate phosphorus compounds incorporating a redox-active ONO amidodiphenoxide scaffold [ONO = N,N-bis(3,5-di-tert-butyl-2-phenoxide)amide] are described. Dichloro- and diphenylphosphoranes, 2·Cl₂ and 2·Ph₂, respectively, are synthesized and crystallographically characterized. Cyclic voltammograms of 2·Cl₂ show only a single irreversible oxidation (E{subscript pa] = +0.83 V vs Cp₂Fe0/+), while the diphenyl analogue 2·Ph2 is reversibly oxidized at lower applied potential (E[subscript 1/2] = +0.47 V vs Cp2Fe[superscript 0/+]). Chemical oxidation of 2·Ph₂ with AgBF₄ produces the corresponding radical cation [2·Ph₂]•+, where electron paramagnetic resonance spectroscopy and density functional theory calculations reveal that the unpaired spin density is largely ligand-based and is highly delocalized throughout the ONO framework of the paramagnetic species. The solid-state structures indicate only minor geometrical changes between the neutral 2·Ph₂ and oxidized [2·Ph₂]•+ species, consistent with fast self-exchange electron transfer, as observed by NMR line-broadening experiments.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/acs.inorgchem.7b00657
