Interconversion of Phosphinyl Radical and Phosphinidene Complexes by Proton Coupled Electron Transfer

The isolable complex [Os(PHMes*)H(PNP)] (Mes*=2,4,6‐(t)Bu(3)C(6)H(3); PNP=N{CHCHP(t)Bu(2)}(2)) exhibits high phosphinyl radical character. This compound offers access to the phosphinidene complex [Os(PMes*)H(PNP)] by P−H proton coupled electron transfer (PCET). The P−H bond dissociation energy (BDE)...

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Autores principales: Abbenseth, Josh, Delony, Daniel, Neben, Marc C., Würtele, Christian, de Bruin, Bas, Schneider, Sven
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2019
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6519162/
https://www.ncbi.nlm.nih.gov/pubmed/30840783
http://dx.doi.org/10.1002/anie.201901470
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author Abbenseth, Josh
Delony, Daniel
Neben, Marc C.
Würtele, Christian
de Bruin, Bas
Schneider, Sven
author_facet Abbenseth, Josh
Delony, Daniel
Neben, Marc C.
Würtele, Christian
de Bruin, Bas
Schneider, Sven
author_sort Abbenseth, Josh
collection PubMed
description The isolable complex [Os(PHMes*)H(PNP)] (Mes*=2,4,6‐(t)Bu(3)C(6)H(3); PNP=N{CHCHP(t)Bu(2)}(2)) exhibits high phosphinyl radical character. This compound offers access to the phosphinidene complex [Os(PMes*)H(PNP)] by P−H proton coupled electron transfer (PCET). The P−H bond dissociation energy (BDE) was determined by isothermal titration calorimetry and supporting DFT computations. The phosphinidene product exhibits electrophilic reactivity as demonstrated by intramolecular C−H activation.
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spelling pubmed-65191622019-05-21 Interconversion of Phosphinyl Radical and Phosphinidene Complexes by Proton Coupled Electron Transfer Abbenseth, Josh Delony, Daniel Neben, Marc C. Würtele, Christian de Bruin, Bas Schneider, Sven Angew Chem Int Ed Engl Communications The isolable complex [Os(PHMes*)H(PNP)] (Mes*=2,4,6‐(t)Bu(3)C(6)H(3); PNP=N{CHCHP(t)Bu(2)}(2)) exhibits high phosphinyl radical character. This compound offers access to the phosphinidene complex [Os(PMes*)H(PNP)] by P−H proton coupled electron transfer (PCET). The P−H bond dissociation energy (BDE) was determined by isothermal titration calorimetry and supporting DFT computations. The phosphinidene product exhibits electrophilic reactivity as demonstrated by intramolecular C−H activation. John Wiley and Sons Inc. 2019-04-01 2019-05-06 /pmc/articles/PMC6519162/ /pubmed/30840783 http://dx.doi.org/10.1002/anie.201901470 Text en © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Communications
Abbenseth, Josh
Delony, Daniel
Neben, Marc C.
Würtele, Christian
de Bruin, Bas
Schneider, Sven
Interconversion of Phosphinyl Radical and Phosphinidene Complexes by Proton Coupled Electron Transfer
title Interconversion of Phosphinyl Radical and Phosphinidene Complexes by Proton Coupled Electron Transfer
title_full Interconversion of Phosphinyl Radical and Phosphinidene Complexes by Proton Coupled Electron Transfer
title_fullStr Interconversion of Phosphinyl Radical and Phosphinidene Complexes by Proton Coupled Electron Transfer
title_full_unstemmed Interconversion of Phosphinyl Radical and Phosphinidene Complexes by Proton Coupled Electron Transfer
title_short Interconversion of Phosphinyl Radical and Phosphinidene Complexes by Proton Coupled Electron Transfer
title_sort interconversion of phosphinyl radical and phosphinidene complexes by proton coupled electron transfer
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6519162/
https://www.ncbi.nlm.nih.gov/pubmed/30840783
http://dx.doi.org/10.1002/anie.201901470
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