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Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium

The reversible reaction of H(2) with a bis-phosphenium complex of chromium provides a rare example of 3d transition metal/phosphenium cooperativity. Photolysis induces the activation of H(2) and yields a spectroscopically detectable phosphenium-stabilized (σ–H(2))-complex, readily showing exchange w...

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Autores principales: Birchall, Nicholas, Feil, Christoph M., Gediga, Michael, Nieger, Martin, Gudat, Dietrich
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8161683/
https://www.ncbi.nlm.nih.gov/pubmed/34094222
http://dx.doi.org/10.1039/d0sc03773g
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author Birchall, Nicholas
Feil, Christoph M.
Gediga, Michael
Nieger, Martin
Gudat, Dietrich
author_facet Birchall, Nicholas
Feil, Christoph M.
Gediga, Michael
Nieger, Martin
Gudat, Dietrich
author_sort Birchall, Nicholas
collection PubMed
description The reversible reaction of H(2) with a bis-phosphenium complex of chromium provides a rare example of 3d transition metal/phosphenium cooperativity. Photolysis induces the activation of H(2) and yields a spectroscopically detectable phosphenium-stabilized (σ–H(2))-complex, readily showing exchange with gaseous H(2) and D(2). Further reaction of this complex affords a phosphine-functionalized metal hydride, representing a unique example of reversible H(2) cleavage across a 3d M[double bond, length as m-dash]P bond. The same species is also accessible via stepwise H(+)/H(−) transfer to the bis-phosphenium complex, and releases H(2) upon heating or irradiation. Dihydrogen transfer from the H(2)-complex to styrene is exploited to demonstrate the first example of promoting hydrogenation with a phosphenium complex.
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spelling pubmed-81616832021-06-04 Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium Birchall, Nicholas Feil, Christoph M. Gediga, Michael Nieger, Martin Gudat, Dietrich Chem Sci Chemistry The reversible reaction of H(2) with a bis-phosphenium complex of chromium provides a rare example of 3d transition metal/phosphenium cooperativity. Photolysis induces the activation of H(2) and yields a spectroscopically detectable phosphenium-stabilized (σ–H(2))-complex, readily showing exchange with gaseous H(2) and D(2). Further reaction of this complex affords a phosphine-functionalized metal hydride, representing a unique example of reversible H(2) cleavage across a 3d M[double bond, length as m-dash]P bond. The same species is also accessible via stepwise H(+)/H(−) transfer to the bis-phosphenium complex, and releases H(2) upon heating or irradiation. Dihydrogen transfer from the H(2)-complex to styrene is exploited to demonstrate the first example of promoting hydrogenation with a phosphenium complex. The Royal Society of Chemistry 2020-08-21 /pmc/articles/PMC8161683/ /pubmed/34094222 http://dx.doi.org/10.1039/d0sc03773g Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Birchall, Nicholas
Feil, Christoph M.
Gediga, Michael
Nieger, Martin
Gudat, Dietrich
Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium
title Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium
title_full Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium
title_fullStr Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium
title_full_unstemmed Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium
title_short Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium
title_sort reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8161683/
https://www.ncbi.nlm.nih.gov/pubmed/34094222
http://dx.doi.org/10.1039/d0sc03773g
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