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dc.contributor.author
Oeschger, Raphael
dc.contributor.author
Bissig, Raphael
dc.contributor.author
Chen, Peter
dc.date.accessioned
2023-07-24T09:55:18Z
dc.date.available
2022-06-22T13:17:49Z
dc.date.available
2022-06-22T13:42:45Z
dc.date.available
2022-07-29T06:56:07Z
dc.date.available
2023-07-24T09:55:18Z
dc.date.issued
2022-06-15
dc.identifier.issn
0002-7863
dc.identifier.issn
1520-5126
dc.identifier.other
10.1021/jacs.2c01641
en_US
dc.identifier.uri
http://hdl.handle.net/20.500.11850/554108
dc.identifier.doi
10.3929/ethz-b-000554108
dc.description.abstract
We report an experimental study, with accompanying DFT calculations, on a series of heterobimetallic complexes with Pd(II) and Cu(I), Ag(I), or Au(I). The isolable pincer complexes are models for the intermediates and transition state for the transmetalation step in Sonagashira and Negishi coupling reactions, among which, according to the DFT calculations, only the transition state has the two metal centers within bonding distance. Furthermore, we report a substituted version of an analogous heterobimetallic complex in which a competing dissociation sets an upper-bound on the strength of the d8-d10 metal-metal bond. Analysis of the structures in the solid state and in solution, and the competitive dissociation experiment in the gas phase, indicate that the dispersion-corrected DFT method used in the study appears to overestimate the strength of the metal-metal interaction, thus distorting the shape of the computed potential energy surface systematically for transmetalation.
en_US
dc.format
application/pdf
en_US
dc.language.iso
en
en_US
dc.publisher
American Chemical Society
en_US
dc.rights.uri
http://rightsstatements.org/page/InC-NC/1.0/
dc.subject
Transmetalation
en_US
dc.subject
DFT computations
en_US
dc.subject
Non-covalent interactions
en_US
dc.subject
Bimetallic
en_US
dc.title
Model compounds for intermediates and transition states in Sonogashira and Negishi coupling: d8-d10 bonds in large heterobimetallic complexes are weaker than computational chemistry predicts.
en_US
dc.type
Journal Article
dc.rights.license
In Copyright - Non-Commercial Use Permitted
dc.date.published
2022-05-31
ethz.journal.title
Journal of the American Chemical Society
ethz.journal.volume
144
en_US
ethz.journal.issue
23
en_US
ethz.journal.abbreviated
J. Am. Chem. Soc.
ethz.pages.start
10330
en_US
ethz.pages.end
10343
en_US
ethz.size
24 p. accepted version; 196 p. supporting information
en_US
ethz.version.deposit
acceptedVersion
en_US
ethz.notes
The first two authors contributed equally to the publication.
en_US
ethz.identifier.wos
ethz.identifier.scopus
ethz.publication.place
Washington, DC
en_US
ethz.publication.status
published
en_US
ethz.leitzahl
ETH Zürich::00002 - ETH Zürich::00012 - Lehre und Forschung::00007 - Departemente::02020 - Dep. Chemie und Angewandte Biowiss. / Dep. of Chemistry and Applied Biosc.::02514 - Laboratorium für Organische Chemie / Laboratory of Organic Chemistry::03425 - Chen, Peter / Chen, Peter
en_US
ethz.leitzahl.certified
ETH Zürich::00002 - ETH Zürich::00012 - Lehre und Forschung::00007 - Departemente::02020 - Dep. Chemie und Angewandte Biowiss. / Dep. of Chemistry and Applied Biosc.::02514 - Laboratorium für Organische Chemie / Laboratory of Organic Chemistry::03425 - Chen, Peter / Chen, Peter
en_US
ethz.date.deposited
2022-06-22T13:17:55Z
ethz.source
FORM
ethz.eth
yes
en_US
ethz.availability
Open access
en_US
ethz.date.embargoend
2023-05-30
ethz.rosetta.installDate
2022-06-22T13:42:51Z
ethz.rosetta.lastUpdated
2024-02-03T01:53:59Z
ethz.rosetta.versionExported
true
ethz.COinS
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