Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides

Handle URI:
http://hdl.handle.net/10754/583970
Title:
Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides
Authors:
Maity, Niladri; Barman, Samir; Callens, Emmanuel; Samantaray, Manoja K.; Abou-Hamad, Edy; Minenkov, Yury; D'Elia, Valerio; Hoffman, Adam S.; Widdifield, Cory M.; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Gates, Bruce C.; Basset, Jean-Marie ( 0000-0003-3166-8882 )
Abstract:
The well-defined single-site silica-supported tungsten complex [([triple bond, length as m-dash]Si–O–)W(Me)5], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at −78 °C into a partially alkylated tungsten hydride, 4, as characterized by 1H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [([triple bond, length as m-dash]Si–O–)WH3(Me)2], as the predominant species at −78 °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between −78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [([triple bond, length as m-dash]Si–O–)WH3([double bond, length as m-dash]CH2)], as determined by solid-state 1H and 13C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.
KAUST Department:
KAUST Catalysis Center (KCC)
Citation:
Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides 2016 Chem. Sci.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Chem. Sci.
Issue Date:
30-Nov-2015
DOI:
10.1039/C5SC03490F
Type:
Article
ISSN:
2041-6520; 2041-6539
Additional Links:
http://xlink.rsc.org/?DOI=C5SC03490F
Appears in Collections:
Articles; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorMaity, Niladrien
dc.contributor.authorBarman, Samiren
dc.contributor.authorCallens, Emmanuelen
dc.contributor.authorSamantaray, Manoja K.en
dc.contributor.authorAbou-Hamad, Edyen
dc.contributor.authorMinenkov, Yuryen
dc.contributor.authorD'Elia, Valerioen
dc.contributor.authorHoffman, Adam S.en
dc.contributor.authorWiddifield, Cory M.en
dc.contributor.authorCavallo, Luigien
dc.contributor.authorGates, Bruce C.en
dc.contributor.authorBasset, Jean-Marieen
dc.date.accessioned2015-12-16T06:43:59Zen
dc.date.available2015-12-16T06:43:59Zen
dc.date.issued2015-11-30en
dc.identifier.citationControlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides 2016 Chem. Sci.en
dc.identifier.issn2041-6520en
dc.identifier.issn2041-6539en
dc.identifier.doi10.1039/C5SC03490Fen
dc.identifier.urihttp://hdl.handle.net/10754/583970en
dc.description.abstractThe well-defined single-site silica-supported tungsten complex [([triple bond, length as m-dash]Si–O–)W(Me)5], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at −78 °C into a partially alkylated tungsten hydride, 4, as characterized by 1H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [([triple bond, length as m-dash]Si–O–)WH3(Me)2], as the predominant species at −78 °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between −78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [([triple bond, length as m-dash]Si–O–)WH3([double bond, length as m-dash]CH2)], as determined by solid-state 1H and 13C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.en
dc.language.isoenen
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.urlhttp://xlink.rsc.org/?DOI=C5SC03490Fen
dc.rightsArchived with thanks to Chem. Sci. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. http://creativecommons.org/licenses/by/3.0/en
dc.titleControlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydridesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalChem. Sci.en
dc.eprint.versionPublisher's Version/PDFen
dc.contributor.institutionDepartment of Materials Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong, Thailanden
dc.contributor.institutionDepartment of Chemical Engineering and Materials Science, University of California at Davis, Davis, USAen
dc.contributor.institutionDepartment of Chemistry, Durham University, Stockton Road, Durham DH1 3LE, UKen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
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