Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study

Handle URI:
http://hdl.handle.net/10754/622965
Title:
Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study
Authors:
Bendjeriou-Sedjerari, Anissa; Sofack-Kreutzer, Julien; Minenkov, Yury; Abou-Hamad, Edy; Hamzaoui, Bilel; Werghi, Baraa; Anjum, Dalaver H.; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Huang, Kuo-Wei ( 0000-0003-1900-2658 ) ; Basset, Jean-Marie ( 0000-0003-3166-8882 )
Abstract:
Designing 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.
KAUST Department:
KAUST Catalysis Center (KCC)
Citation:
Bendjeriou-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.
Publisher:
Wiley-Blackwell
Journal:
Angewandte Chemie International Edition
KAUST Grant Number:
CRG_R2_13_BASS_KAUST_1
Issue Date:
11-Aug-2016
DOI:
10.1002/anie.201605934; 10.1002/ange.201605934
PubMed ID:
27514022
Type:
Article
ISSN:
1433-7851
Sponsors:
This 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.
Additional Links:
http://onlinelibrary.wiley.com/doi/10.1002/anie.201605934/full
Appears in Collections:
Articles; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorBendjeriou-Sedjerari, Anissaen
dc.contributor.authorSofack-Kreutzer, Julienen
dc.contributor.authorMinenkov, Yuryen
dc.contributor.authorAbou-Hamad, Edyen
dc.contributor.authorHamzaoui, Bilelen
dc.contributor.authorWerghi, Baraaen
dc.contributor.authorAnjum, Dalaver H.en
dc.contributor.authorCavallo, Luigien
dc.contributor.authorHuang, Kuo-Weien
dc.contributor.authorBasset, Jean-Marieen
dc.date.accessioned2017-03-06T08:41:24Z-
dc.date.available2017-03-06T08:41:24Z-
dc.date.issued2016-08-11en
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.en
dc.identifier.issn1433-7851en
dc.identifier.pmid27514022en
dc.identifier.doi10.1002/anie.201605934en
dc.identifier.doi10.1002/ange.201605934en
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.en
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.en
dc.publisherWiley-Blackwellen
dc.relation.urlhttp://onlinelibrary.wiley.com/doi/10.1002/anie.201605934/fullen
dc.subjectchelating ligandsen
dc.subject-H exchangeen
dc.subjectSBA15 silicaen
dc.subjectsurface organometallic chemistryen
dc.subjecttautomerizationen
dc.titleTungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Studyen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalAngewandte Chemie International Editionen
kaust.authorBendjeriou-Sedjerari, Anissaen
kaust.authorSofack-Kreutzer, Julienen
kaust.authorMinenkov, Yuryen
kaust.authorAbou-Hamad, Edyen
kaust.authorHamzaoui, Bilelen
kaust.authorWerghi, Baraaen
kaust.authorAnjum, Dalaver H.en
kaust.authorCavallo, Luigien
kaust.authorHuang, Kuo-Weien
kaust.authorBasset, Jean-Marieen
kaust.grant.numberCRG_R2_13_BASS_KAUST_1en

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