WMe6 tamed by silica: Si-O-WMe5 as an efficient, well-defined species for alkane metathesis, leading to the observation of a supported W-methyl/methylidyne species

Manoja Samantaray; Emmanuel Callens; Edy Abou-Hamad; Aaron J. Rossini; Cory M. Widdifield; Raju Dey; Lyndon Emsley; Jean-Marie Basset

doi:10.1021/ja410747g

WMe6 tamed by silica: Si-O-WMe5 as an efficient, well-defined species for alkane metathesis, leading to the observation of a supported W-methyl/methylidyne species

Manoja Samantaray, Emmanuel Callens, Edy Abou-Hamad, Aaron J. Rossini, Cory M. Widdifield, Raju Dey, Lyndon Emsley, Jean-Marie Basset

Research output: Contribution to journal › Article › peer-review

82 Scopus citations

Abstract

The synthesis and full characterization of a well-defined silica-supported ≡Si-O-W(Me)5 species is reported. Under an inert atmosphere, it is a stable material at moderate temperature, whereas the homoleptic parent complex decomposes above -20 °C, demonstrating the stabilizing effect of immobilization of the molecular complex. Above 70 °C the grafted complex converts into the two methylidyne surface complexes [(≡SiO-)W(≡CH) Me2] and [(≡SiO-)2W(≡CH)Me]. All of these silica-supported complexes are active precursors for propane metathesis reactions. © 2013 American Chemical Society.

Original language	English (US)
Pages (from-to)	1054-1061
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	136
Issue number	3
DOIs	https://doi.org/10.1021/ja410747g
State	Published - Jan 10 2014

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: The authors acknowledge the KAUST Nuclear Magnetic Resonance Core Lab and technical assistance of Dr. Kazuo Yamauchi. The authors also thank Dr. Nassima Riache for her fruitful discussions. Mr. Benoit Vincenti is thanked for inert-atmosphere sample preparation prior to solid-state NMR experiments upon 2. A.J.R. acknowledges support from an EU Marie-Curie IIF fellowship (PIIF-GA-2010-274574). C.M.W. acknowledges the Natural Sciences and Engineering Council of Canada (NSERC) for a postdoctoral fellowship. Computational resources for DFT calculations were provided by the Pole Scientifique de Modelisation Numerique (PSMN). This work was supported by funds from King Abdullah University of Science and Technology.

ASJC Scopus subject areas

Biochemistry
Colloid and Surface Chemistry
General Chemistry
Catalysis

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10.1021/ja410747g

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Samantaray, M., Callens, E., Abou-Hamad, E., Rossini, A. J., Widdifield, C. M., Dey, R., Emsley, L., & Basset, J.-M. (2014). WMe6 tamed by silica: Si-O-WMe5 as an efficient, well-defined species for alkane metathesis, leading to the observation of a supported W-methyl/methylidyne species. Journal of the American Chemical Society, 136(3), 1054-1061. https://doi.org/10.1021/ja410747g

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title = "WMe6 tamed by silica: Si-O-WMe5 as an efficient, well-defined species for alkane metathesis, leading to the observation of a supported W-methyl/methylidyne species",

abstract = "The synthesis and full characterization of a well-defined silica-supported ≡Si-O-W(Me)5 species is reported. Under an inert atmosphere, it is a stable material at moderate temperature, whereas the homoleptic parent complex decomposes above -20 °C, demonstrating the stabilizing effect of immobilization of the molecular complex. Above 70 °C the grafted complex converts into the two methylidyne surface complexes [(≡SiO-)W(≡CH) Me2] and [(≡SiO-)2W(≡CH)Me]. All of these silica-supported complexes are active precursors for propane metathesis reactions. {\textcopyright} 2013 American Chemical Society.",

author = "Manoja Samantaray and Emmanuel Callens and Edy Abou-Hamad and Rossini, {Aaron J.} and Widdifield, {Cory M.} and Raju Dey and Lyndon Emsley and Jean-Marie Basset",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: The authors acknowledge the KAUST Nuclear Magnetic Resonance Core Lab and technical assistance of Dr. Kazuo Yamauchi. The authors also thank Dr. Nassima Riache for her fruitful discussions. Mr. Benoit Vincenti is thanked for inert-atmosphere sample preparation prior to solid-state NMR experiments upon 2. A.J.R. acknowledges support from an EU Marie-Curie IIF fellowship (PIIF-GA-2010-274574). C.M.W. acknowledges the Natural Sciences and Engineering Council of Canada (NSERC) for a postdoctoral fellowship. Computational resources for DFT calculations were provided by the Pole Scientifique de Modelisation Numerique (PSMN). This work was supported by funds from King Abdullah University of Science and Technology.",

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language = "English (US)",

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Samantaray, M, Callens, E, Abou-Hamad, E, Rossini, AJ, Widdifield, CM, Dey, R, Emsley, L & Basset, J-M 2014, 'WMe6 tamed by silica: Si-O-WMe5 as an efficient, well-defined species for alkane metathesis, leading to the observation of a supported W-methyl/methylidyne species', Journal of the American Chemical Society, vol. 136, no. 3, pp. 1054-1061. https://doi.org/10.1021/ja410747g

WMe6 tamed by silica: Si-O-WMe5 as an efficient, well-defined species for alkane metathesis, leading to the observation of a supported W-methyl/methylidyne species. / Samantaray, Manoja; Callens, Emmanuel; Abou-Hamad, Edy et al.
In: Journal of the American Chemical Society, Vol. 136, No. 3, 10.01.2014, p. 1054-1061.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - WMe6 tamed by silica: Si-O-WMe5 as an efficient, well-defined species for alkane metathesis, leading to the observation of a supported W-methyl/methylidyne species

AU - Samantaray, Manoja

AU - Callens, Emmanuel

AU - Abou-Hamad, Edy

AU - Rossini, Aaron J.

AU - Widdifield, Cory M.

AU - Dey, Raju

AU - Emsley, Lyndon

AU - Basset, Jean-Marie

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: The authors acknowledge the KAUST Nuclear Magnetic Resonance Core Lab and technical assistance of Dr. Kazuo Yamauchi. The authors also thank Dr. Nassima Riache for her fruitful discussions. Mr. Benoit Vincenti is thanked for inert-atmosphere sample preparation prior to solid-state NMR experiments upon 2. A.J.R. acknowledges support from an EU Marie-Curie IIF fellowship (PIIF-GA-2010-274574). C.M.W. acknowledges the Natural Sciences and Engineering Council of Canada (NSERC) for a postdoctoral fellowship. Computational resources for DFT calculations were provided by the Pole Scientifique de Modelisation Numerique (PSMN). This work was supported by funds from King Abdullah University of Science and Technology.

PY - 2014/1/10

Y1 - 2014/1/10

N2 - The synthesis and full characterization of a well-defined silica-supported ≡Si-O-W(Me)5 species is reported. Under an inert atmosphere, it is a stable material at moderate temperature, whereas the homoleptic parent complex decomposes above -20 °C, demonstrating the stabilizing effect of immobilization of the molecular complex. Above 70 °C the grafted complex converts into the two methylidyne surface complexes [(≡SiO-)W(≡CH) Me2] and [(≡SiO-)2W(≡CH)Me]. All of these silica-supported complexes are active precursors for propane metathesis reactions. © 2013 American Chemical Society.

AB - The synthesis and full characterization of a well-defined silica-supported ≡Si-O-W(Me)5 species is reported. Under an inert atmosphere, it is a stable material at moderate temperature, whereas the homoleptic parent complex decomposes above -20 °C, demonstrating the stabilizing effect of immobilization of the molecular complex. Above 70 °C the grafted complex converts into the two methylidyne surface complexes [(≡SiO-)W(≡CH) Me2] and [(≡SiO-)2W(≡CH)Me]. All of these silica-supported complexes are active precursors for propane metathesis reactions. © 2013 American Chemical Society.

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UR - https://pubs.acs.org/doi/10.1021/ja410747g

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DO - 10.1021/ja410747g

M3 - Article

C2 - 24369727

SN - 0002-7863

VL - 136

SP - 1054

EP - 1061

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 3

ER -

WMe6 tamed by silica: Si-O-WMe5 as an efficient, well-defined species for alkane metathesis, leading to the observation of a supported W-methyl/methylidyne species

Abstract

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