dc.date.accessioned | 2018-09-12T10:50:04Z | |
dc.date.available | 2018-09-12T10:50:04Z | |
dc.date.created | 2018-03-26T12:04:26Z | |
dc.date.issued | 2018 | |
dc.identifier.citation | Gordon, Christopher P. Yamamoto, Keishi Searles, Keith Shirase, Satoru Andersen, Richard A Eisenstein, Odile Copéret, Christophe . Metal alkyls programmed to generate metal alkylidenes by a-H abstraction: prognosis from NMR chemical shift. Chemical Science. 2018, 9, 1912 | |
dc.identifier.uri | http://hdl.handle.net/10852/64657 | |
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.language | EN | |
dc.rights | Attribution 3.0 Unported | |
dc.rights.uri | https://creativecommons.org/licenses/by/3.0/ | |
dc.title | Metal alkyls programmed to generate metal alkylidenes by a-H abstraction: prognosis from NMR chemical shift | en_US |
dc.type | Journal article | en_US |
dc.creator.author | Gordon, Christopher P. | |
dc.creator.author | Yamamoto, Keishi | |
dc.creator.author | Searles, Keith | |
dc.creator.author | Shirase, Satoru | |
dc.creator.author | Andersen, Richard A | |
dc.creator.author | Eisenstein, Odile | |
dc.creator.author | Copéret, Christophe | |
cristin.unitcode | 185,15,12,70 | |
cristin.unitname | Hylleraas-senteret | |
cristin.ispublished | true | |
cristin.fulltext | original | |
cristin.qualitycode | 1 | |
dc.identifier.cristin | 1575703 | |
dc.identifier.bibliographiccitation | info:ofi/fmt:kev:mtx:ctx&ctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Chemical Science&rft.volume=9&rft.spage=1912&rft.date=2018 | |
dc.identifier.jtitle | Chemical Science | |
dc.identifier.volume | 9 | |
dc.identifier.startpage | 1912 | |
dc.identifier.doi | http://dx.doi.org/10.1039/c7sc05039a | |
dc.identifier.urn | URN:NBN:no-67189 | |
dc.type.document | Tidsskriftartikkel | en_US |
dc.type.peerreviewed | Peer reviewed | |
dc.source.issn | 2041-6520 | |
dc.identifier.fulltext | Fulltext https://www.duo.uio.no/bitstream/handle/10852/64657/1/M-alkyl-NMR%2BCOperet%2BAndersen.pdf | |
dc.type.version | PublishedVersion | |
dc.relation.project | NFR/262695 | |