Tetracopper σ-Bound μ-Acetylide and -Diyne Units Stabilized by a Naphthyridine-based Dinucleating Ligand

Reactions of a dicopper(I) tert-butoxide complex with alkynes possessing boryl or silyl capping groups resulted in formation of unprecedented tetracopper(I) μ-acetylide/diyne complexes that were characterized by NMR and UV/Vis spectroscopy, mass spectrometry and single-crystal X-ray diffraction. The...

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Autores: Ríos Moreno, Pablo, See, Matthew S., Handford, Rex C., Cooper, Jason K., Don Tilley, T.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Universidad de Sevilla (US)
Repositorio:idUS. Depósito de Investigación de la Universidad de Sevilla
OAI Identifier:oai:idus.us.es:11441/158088
Acceso en línea:https://hdl.handle.net/11441/158088
https://doi.org/10.1002/anie.202310307
Access Level:acceso abierto
Palabra clave:Acetylide
Alkynes
Naphthyridine
Tetracopper
σ-Bonding
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spelling Tetracopper σ-Bound μ-Acetylide and -Diyne Units Stabilized by a Naphthyridine-based Dinucleating LigandRíos Moreno, PabloSee, Matthew S.Handford, Rex C.Cooper, Jason K.Don Tilley, T.AcetylideAlkynesNaphthyridineTetracopperσ-BondingReactions of a dicopper(I) tert-butoxide complex with alkynes possessing boryl or silyl capping groups resulted in formation of unprecedented tetracopper(I) μ-acetylide/diyne complexes that were characterized by NMR and UV/Vis spectroscopy, mass spectrometry and single-crystal X-ray diffraction. These compounds possess an unusual μ4-η1:η1:η1:η1 coordination mode for the bridging organic fragment, enforced by the rigid and dinucleating nature of the ligand utilized. Thus, the central π system remains unperturbed and accessible for subsequent reactivity and modification. This has been corroborated by addition of a fifth copper atom, giving rise to a pentacopper acetylide complex. This work may provide a new approach by which metal-metal cooperativity can be exploited in the transformation of acetylide and diyne groups to a variety of substrates, or as a starting point for the controlled synthesis of copper(I) alkyne-containing clusters.Department of Energy DE- AC02-05CH11231European Union 841154National Institutes of Health 10-RR027172University of California SRR023679A, S10OD024998, 1S10RR016634-0, S10OD02353Wiley-BlackwellQuímica InorgánicaDepartment of Energy. United StatesEuropean Union (UE). H2020National Institutes of Health. United StatesUniversity of California, Berkeley2023info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfapplication/pdfhttps://hdl.handle.net/11441/158088https://doi.org/10.1002/anie.202310307reponame:idUS. Depósito de Investigación de la Universidad de Sevillainstname:Universidad de Sevilla (US)InglésAngewandte Chemie - International Edition, 62 (45), e202310307.DE- AC02-05CH1123184115410-RR027172SRR023679AS10OD0249981S10RR016634-0S10OD02353https://doi.org/10.1002/anie.202310307info:eu-repo/semantics/openAccessoai:idus.us.es:11441/1580882026-06-17T12:51:07Z
dc.title.none.fl_str_mv Tetracopper σ-Bound μ-Acetylide and -Diyne Units Stabilized by a Naphthyridine-based Dinucleating Ligand
title Tetracopper σ-Bound μ-Acetylide and -Diyne Units Stabilized by a Naphthyridine-based Dinucleating Ligand
spellingShingle Tetracopper σ-Bound μ-Acetylide and -Diyne Units Stabilized by a Naphthyridine-based Dinucleating Ligand
Ríos Moreno, Pablo
Acetylide
Alkynes
Naphthyridine
Tetracopper
σ-Bonding
title_short Tetracopper σ-Bound μ-Acetylide and -Diyne Units Stabilized by a Naphthyridine-based Dinucleating Ligand
title_full Tetracopper σ-Bound μ-Acetylide and -Diyne Units Stabilized by a Naphthyridine-based Dinucleating Ligand
title_fullStr Tetracopper σ-Bound μ-Acetylide and -Diyne Units Stabilized by a Naphthyridine-based Dinucleating Ligand
title_full_unstemmed Tetracopper σ-Bound μ-Acetylide and -Diyne Units Stabilized by a Naphthyridine-based Dinucleating Ligand
title_sort Tetracopper σ-Bound μ-Acetylide and -Diyne Units Stabilized by a Naphthyridine-based Dinucleating Ligand
dc.creator.none.fl_str_mv Ríos Moreno, Pablo
See, Matthew S.
Handford, Rex C.
Cooper, Jason K.
Don Tilley, T.
author Ríos Moreno, Pablo
author_facet Ríos Moreno, Pablo
See, Matthew S.
Handford, Rex C.
Cooper, Jason K.
Don Tilley, T.
author_role author
author2 See, Matthew S.
Handford, Rex C.
Cooper, Jason K.
Don Tilley, T.
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Química Inorgánica
Department of Energy. United States
European Union (UE). H2020
National Institutes of Health. United States
University of California, Berkeley
dc.subject.none.fl_str_mv Acetylide
Alkynes
Naphthyridine
Tetracopper
σ-Bonding
topic Acetylide
Alkynes
Naphthyridine
Tetracopper
σ-Bonding
description Reactions of a dicopper(I) tert-butoxide complex with alkynes possessing boryl or silyl capping groups resulted in formation of unprecedented tetracopper(I) μ-acetylide/diyne complexes that were characterized by NMR and UV/Vis spectroscopy, mass spectrometry and single-crystal X-ray diffraction. These compounds possess an unusual μ4-η1:η1:η1:η1 coordination mode for the bridging organic fragment, enforced by the rigid and dinucleating nature of the ligand utilized. Thus, the central π system remains unperturbed and accessible for subsequent reactivity and modification. This has been corroborated by addition of a fifth copper atom, giving rise to a pentacopper acetylide complex. This work may provide a new approach by which metal-metal cooperativity can be exploited in the transformation of acetylide and diyne groups to a variety of substrates, or as a starting point for the controlled synthesis of copper(I) alkyne-containing clusters.
publishDate 2023
dc.date.none.fl_str_mv 2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/11441/158088
https://doi.org/10.1002/anie.202310307
url https://hdl.handle.net/11441/158088
https://doi.org/10.1002/anie.202310307
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Angewandte Chemie - International Edition, 62 (45), e202310307.
DE- AC02-05CH11231
841154
10-RR027172
SRR023679A
S10OD024998
1S10RR016634-0
S10OD02353
https://doi.org/10.1002/anie.202310307
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Wiley-Blackwell
publisher.none.fl_str_mv Wiley-Blackwell
dc.source.none.fl_str_mv reponame:idUS. Depósito de Investigación de la Universidad de Sevilla
instname:Universidad de Sevilla (US)
instname_str Universidad de Sevilla (US)
reponame_str idUS. Depósito de Investigación de la Universidad de Sevilla
collection idUS. Depósito de Investigación de la Universidad de Sevilla
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300724

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