Stable Open-Shell Phosphorane Based on a Redox-Active Amidodiphenoxide Scaffold

Allen J. Pistner, Hye Won Moon, Alexey Silakov, Hemant P. Yennawar, Alexander T. Radosevich

Research output: Contribution to journalReview article

7 Citations (Scopus)

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 (Epa = +0.83 V vs Cp2Fe0/+), while the diphenyl analogue 2·Ph2 is reversibly oxidized at lower applied potential (E1/2 = +0.47 V vs Cp2Fe0/+). 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.

Original languageEnglish (US)
Pages (from-to)8661-8668
Number of pages8
JournalInorganic chemistry
Volume56
Issue number15
DOIs
StatePublished - Aug 7 2017

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Phosphoranes
Scaffolds
Phosphorus Compounds
phosphorus compounds
Oxidation
oxidation
Amides
amides
Density functional theory
Paramagnetic resonance
Cations
electron paramagnetic resonance
electron transfer
reactivity
Nuclear magnetic resonance
Spectroscopy
analogs
density functional theory
Ligands
solid state

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Pistner, Allen J. ; Moon, Hye Won ; Silakov, Alexey ; Yennawar, Hemant P. ; Radosevich, Alexander T. / Stable Open-Shell Phosphorane Based on a Redox-Active Amidodiphenoxide Scaffold. In: Inorganic chemistry. 2017 ; Vol. 56, No. 15. pp. 8661-8668.
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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 (Epa = +0.83 V vs Cp2Fe0/+), while the diphenyl analogue 2·Ph2 is reversibly oxidized at lower applied potential (E1/2 = +0.47 V vs Cp2Fe0/+). 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.",
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Stable Open-Shell Phosphorane Based on a Redox-Active Amidodiphenoxide Scaffold. / Pistner, Allen J.; Moon, Hye Won; Silakov, Alexey; Yennawar, Hemant P.; Radosevich, Alexander T.

In: Inorganic chemistry, Vol. 56, No. 15, 07.08.2017, p. 8661-8668.

Research output: Contribution to journalReview article

TY - JOUR

T1 - Stable Open-Shell Phosphorane Based on a Redox-Active Amidodiphenoxide Scaffold

AU - Pistner, Allen J.

AU - Moon, Hye Won

AU - Silakov, Alexey

AU - Yennawar, Hemant P.

AU - Radosevich, Alexander T.

PY - 2017/8/7

Y1 - 2017/8/7

N2 - 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 (Epa = +0.83 V vs Cp2Fe0/+), while the diphenyl analogue 2·Ph2 is reversibly oxidized at lower applied potential (E1/2 = +0.47 V vs Cp2Fe0/+). 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.

AB - 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 (Epa = +0.83 V vs Cp2Fe0/+), while the diphenyl analogue 2·Ph2 is reversibly oxidized at lower applied potential (E1/2 = +0.47 V vs Cp2Fe0/+). 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.

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