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Metal alkyls programmed to generate metal alkylidenes by α-H abstraction: prognosis from NMR chemical shift.
Journal article

Metal alkyls programmed to generate metal alkylidenes by α-H abstraction: prognosis from NMR chemical shift.

  • Gordon CP Department of Chemistry and Applied Biosciences , ETH Zürich , Vladimir Prelog Weg 1-5 , 8093 , Zürich , Switzerland . Email: ccoperet@ethz.ch.
  • Yamamoto K Department of Chemistry and Applied Biosciences , ETH Zürich , Vladimir Prelog Weg 1-5 , 8093 , Zürich , Switzerland . Email: ccoperet@ethz.ch.
  • Searles K Department of Chemistry and Applied Biosciences , ETH Zürich , Vladimir Prelog Weg 1-5 , 8093 , Zürich , Switzerland . Email: ccoperet@ethz.ch.
  • Shirase S Department of Chemistry and Applied Biosciences , ETH Zürich , Vladimir Prelog Weg 1-5 , 8093 , Zürich , Switzerland . Email: ccoperet@ethz.ch.
  • Andersen RA Department of Chemistry , University of California , Berkeley , California 94720 , USA . Email: raandersen@lbl.gov.
  • Eisenstein O Institut Charles Gerhardt , UMR 5253 CNRS-UM-ENSCM , Université de Montpellier , 34095 Montpellier , France . Email: odile.eisenstein@univ-montp2.fr.
  • Copéret C Department of Chemistry and Applied Biosciences , ETH Zürich , Vladimir Prelog Weg 1-5 , 8093 , Zürich , Switzerland . Email: ccoperet@ethz.ch.
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  • 2018-04-21
Published in:
  • Chemical science. - 2018
General Chemistry
English 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.
Language
  • English
Open access status
gold
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https://sonar.ch/global/documents/61377
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