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dc.contributor.author
Gordon, Christopher
dc.contributor.author
Yamamoto, Keishi
dc.contributor.author
Searles, Keith
dc.contributor.author
Shirase, Satoru
dc.contributor.author
Andersen, Richard A.
dc.contributor.author
Eisenstein, Odile
dc.contributor.author
Copéret, Christophe
dc.date.accessioned
2018-03-06T10:06:54Z
dc.date.available
2018-02-27T03:37:22Z
dc.date.available
2018-03-06T10:06:54Z
dc.date.issued
2018-02
dc.identifier.issn
2041-6520
dc.identifier.issn
2041-6539
dc.identifier.other
10.1039/c7sc05039a
en_US
dc.identifier.uri
http://hdl.handle.net/20.500.11850/244461
dc.identifier.doi
10.3929/ethz-b-000244461
dc.description.abstract
Metal alkylidenes, which are key organometallic intermediates in reactions such as olefination or alkene and alkane metathesis, are typically generated from metal dialkyl compounds [M](CH2R)2 that show distinctively deshielded chemical shifts for their α-carbons. Experimental solid-state NMR measurements combined with DFT/ZORA calculations and a chemical shift tensor analysis reveal that this remarkable deshielding originates from an empty metal d-orbital oriented in the M–Cα–Cα′ plane, interacting with the Cα p-orbital lying in the same plane. This π-type interaction inscribes some alkylidene character into Cα that favors alkylidene generation via α-H abstraction. The extent of the deshielding and the anisotropy of the alkyl chemical shift tensors distinguishes [M](CH2R)2 compounds that form alkylidenes from those that do not, relating the reactivity to molecular orbitals of the respective molecules. The α-carbon chemical shifts and tensor orientations thus predict the reactivity of metal alkyl compounds towards alkylidene generation.
en_US
dc.format
application/pdf
en_US
dc.language.iso
en
en_US
dc.publisher
Royal Society of Chemistry
en_US
dc.rights.uri
http://creativecommons.org/licenses/by/3.0/
dc.title
Metal alkyls programmed to generate metal alkylidenes by α-H abstraction: Prognosis from NMR chemical shift
en_US
dc.type
Journal Article
dc.rights.license
Creative Commons Attribution 3.0 Unported
dc.date.published
2018-01-05
ethz.journal.title
Chemical Science
ethz.journal.volume
9
en_US
ethz.journal.issue
7
en_US
ethz.journal.abbreviated
Chem. Sci.
ethz.pages.start
1912
en_US
ethz.pages.end
1918
en_US
ethz.version.deposit
publishedVersion
en_US
ethz.identifier.wos
ethz.identifier.scopus
ethz.publication.place
Cambridge
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.::02513 - Laboratorium für Anorganische Chemie / Laboratory of Inorganic Chemistry::03872 - Copéret, Christophe / Copéret, Christophe
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.::02513 - Laboratorium für Anorganische Chemie / Laboratory of Inorganic Chemistry::03872 - Copéret, Christophe / Copéret, Christophe
ethz.date.deposited
2018-02-27T03:37:31Z
ethz.source
SCOPUS
ethz.eth
yes
en_US
ethz.availability
Open access
en_US
ethz.rosetta.installDate
2018-03-06T10:06:58Z
ethz.rosetta.lastUpdated
2022-03-28T19:20:07Z
ethz.rosetta.versionExported
true
ethz.COinS
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