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dc.contributor.authorBendjeriou-Sedjerari, Anissa
dc.contributor.authorSofack-Kreutzer, Julien
dc.contributor.authorMinenkov, Yury
dc.contributor.authorAbou-Hamad, Edy
dc.contributor.authorHamzaoui, Bilel
dc.contributor.authorWerghi, Baraa
dc.contributor.authorAnjum, Dalaver H.
dc.contributor.authorCavallo, Luigi
dc.contributor.authorHuang, Kuo-Wei
dc.contributor.authorBasset, Jean-Marie
dc.date.accessioned2017-03-06T08:41:24Z
dc.date.available2017-03-06T08:41:24Z
dc.date.issued2016-08-11
dc.identifier.citationBendjeriou-Sedjerari A, Sofack-Kreutzer J, Minenkov Y, Abou-Hamad E, Hamzaoui B, et al. (2016) Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study. Angewandte Chemie International Edition 55: 11162–11166. Available: http://dx.doi.org/10.1002/anie.201605934.
dc.identifier.issn1433-7851
dc.identifier.pmid27514022
dc.identifier.doi10.1002/anie.201605934
dc.identifier.doi10.1002/ange.201605934
dc.identifier.urihttp://hdl.handle.net/10754/622965
dc.description.abstractDesigning supported well-defined bis(carbene) complexes remains a key challenge in heterogeneous catalysis. The reaction of W(CtBu)(CH(2)tBu)(3) with amine-modified mesoporous SBA15 silica, which has vicinal silanol/silylamine pairs [(SiOH)(SiNH2)], leads to [(SiNH2-)(SiO-)W(CHtBu)(CH(2)tBu)(2)] and [(SiNH2-)(SiO-)W(=CHtBu)(2)(CH(2)tBu). Variable temperature, H-1-H-1 2D double-quantum, H-1-C-13 HETCOR, and HETCOR with spin diffusion solid-state NMR spectroscopy demonstrate tautomerization between the alkyl alkylidyne and the bis(alkylidene) on the SBA15 surface. Such equilibrium is possible through the coordination of W to the surface [(Si-OH)(Si-NH2)] groups, which act as a [N,O] pincer ligand. DFT calculations provide a rationalization for the surface-complex tautomerization and support the experimental results. This direct observation of such a process shows the strong similarity between molecular mechanisms in homogeneous and heterogeneous catalysis. In propane metathesis (at 150 degrees C), the tungsten bis(carbene) tautomer is favorable, with a turnover number (TON) of 262. It is the highest TON among all the tungsten alkyl-supported catalysts.
dc.description.sponsorshipThis work received support from the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under Award No. CRG_R2_13_BASS_KAUST_1.
dc.publisherWiley-Blackwell
dc.relation.urlhttp://onlinelibrary.wiley.com/doi/10.1002/anie.201605934/full
dc.subjectchelating ligands
dc.subject-H exchange
dc.subjectSBA15 silica
dc.subjectsurface organometallic chemistry
dc.subjecttautomerization
dc.titleTungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentElectron Microscopy
dc.contributor.departmentHomogeneous Catalysis Laboratory (HCL)
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalAngewandte Chemie International Edition
kaust.personBendjeriou-Sedjerari, Anissa
kaust.personSofack-Kreutzer, Julien
kaust.personMinenkov, Yury
kaust.personAbou-Hamad, Edy
kaust.personHamzaoui, Bilel
kaust.personWerghi, Baraa
kaust.personAnjum, Dalaver H.
kaust.personCavallo, Luigi
kaust.personHuang, Kuo-Wei
kaust.personBasset, Jean-Marie
kaust.grant.numberCRG_R2_13_BASS_KAUST_1
dc.date.published-online2016-08-11
dc.date.published-print2016-09-05


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