A Silica-Supported Monoalkylated Tungsten Dioxo Complex Catalyst for Olefin Metathesis

Niladri Maity; Samir Barman; Yury Minenkov; Samy Ould-Chikh; Edy Abou-Hamad; Tao Ma; Ziyauddin S. Qureshi; Luigi Cavallo; Valerio D'Elia; Bruce C. Gates; Jean Marie Basset

doi:10.1021/acscatal.7b04304

A Silica-Supported Monoalkylated Tungsten Dioxo Complex Catalyst for Olefin Metathesis

Niladri Maity
, Samir Barman
, Yury Minenkov
, Samy Ould-Chikh
, Edy Abou-Hamad
, Tao Ma
, Ziyauddin S. Qureshi
, Luigi Cavallo
, Valerio D'Elia^*
, Bruce C. Gates
, Jean Marie Basset

^*Corresponding author for this work

Interdisciplinary Research Center for Refining and Advanced Chemicals

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

48 Scopus citations

Abstract

A well-defined silica-supported monoalkylated tungsten dioxo complex [(Si-O-)W(=O)₂(CH₂-^tBu)] was prepared by treatment of highly dehydroxylated silica (SiO_2-700: silica treated at 700 °C under high vacuum) with an ionic precursor complex [NEt₄][W(=O)₃(CH₂-^tBu)]. The identity of the resulting neutral monoalkylated tungsten dioxo surface complex was established by means of elemental microanalysis and spectroscopic studies (IR, solid-state NMR, Raman, and X-ray absorption spectroscopies). The supported tungsten complex was found to act as a precatalyst for the self-metathesis of 1-octene in a batch reactor. The mechanistic implications of this reaction are discussed with the support of DFT calculations highlighting the potential occurrence of thus-far unexplored mechanistic pathways.

Original language	English
Pages (from-to)	2715-2729
Number of pages	15
Journal	ACS Catalysis
Volume	8
Issue number	4
DOIs	https://doi.org/10.1021/acscatal.7b04304
State	Published - 6 Apr 2018

Bibliographical note

Funding Information:
V.D.E. thanks the Thailand Research Fund (Grant No. RSA6080059) for funding. Notes The authors declare no competing financial interest.

Funding Information:
The research was supported by the King Abdullah University of Science and Technology (KAUST). The authors acknowledge Dr. Christian G. Canlas and Erjia Guan for their assistance. The work at the University of California was supported by the U.S. Department of Energy (DOE, Basic Energy Sciences DE-FG02-04ER15513). We acknowledge the European Synchrotron Radiation Facility for provision of synchrotron radiation facilities, and we would like to thank Antonio Aguilar for assistance in using beamline BM30 B.

Publisher Copyright:
© 2018 American Chemical Society.

Keywords

Olefin metathesis
mechanistic study
metallacyclobutane intermediate
tungsten alkylidene
tungsten dioxo complex

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1021/acscatal.7b04304

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title = "A Silica-Supported Monoalkylated Tungsten Dioxo Complex Catalyst for Olefin Metathesis",

abstract = "A well-defined silica-supported monoalkylated tungsten dioxo complex [(Si-O-)W(=O)2(CH2-tBu)] was prepared by treatment of highly dehydroxylated silica (SiO2-700: silica treated at 700 °C under high vacuum) with an ionic precursor complex [NEt4][W(=O)3(CH2-tBu)]. The identity of the resulting neutral monoalkylated tungsten dioxo surface complex was established by means of elemental microanalysis and spectroscopic studies (IR, solid-state NMR, Raman, and X-ray absorption spectroscopies). The supported tungsten complex was found to act as a precatalyst for the self-metathesis of 1-octene in a batch reactor. The mechanistic implications of this reaction are discussed with the support of DFT calculations highlighting the potential occurrence of thus-far unexplored mechanistic pathways.",

keywords = "Olefin metathesis, mechanistic study, metallacyclobutane intermediate, tungsten alkylidene, tungsten dioxo complex",

author = "Niladri Maity and Samir Barman and Yury Minenkov and Samy Ould-Chikh and Edy Abou-Hamad and Tao Ma and Qureshi, \{Ziyauddin S.\} and Luigi Cavallo and Valerio D'Elia and Gates, \{Bruce C.\} and Basset, \{Jean Marie\}",

note = "Funding Information: V.D.E. thanks the Thailand Research Fund (Grant No. RSA6080059) for funding. Notes The authors declare no competing financial interest. Funding Information: The research was supported by the King Abdullah University of Science and Technology (KAUST). The authors acknowledge Dr. Christian G. Canlas and Erjia Guan for their assistance. The work at the University of California was supported by the U.S. Department of Energy (DOE, Basic Energy Sciences DE-FG02-04ER15513). We acknowledge the European Synchrotron Radiation Facility for provision of synchrotron radiation facilities, and we would like to thank Antonio Aguilar for assistance in using beamline BM30 B. Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

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day = "6",

doi = "10.1021/acscatal.7b04304",

language = "English",

volume = "8",

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journal = "ACS Catalysis",

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AU - Maity, Niladri

AU - Barman, Samir

AU - Minenkov, Yury

AU - Ould-Chikh, Samy

AU - Abou-Hamad, Edy

AU - Ma, Tao

AU - Qureshi, Ziyauddin S.

AU - Cavallo, Luigi

AU - D'Elia, Valerio

AU - Gates, Bruce C.

AU - Basset, Jean Marie

N1 - Funding Information: V.D.E. thanks the Thailand Research Fund (Grant No. RSA6080059) for funding. Notes The authors declare no competing financial interest. Funding Information: The research was supported by the King Abdullah University of Science and Technology (KAUST). The authors acknowledge Dr. Christian G. Canlas and Erjia Guan for their assistance. The work at the University of California was supported by the U.S. Department of Energy (DOE, Basic Energy Sciences DE-FG02-04ER15513). We acknowledge the European Synchrotron Radiation Facility for provision of synchrotron radiation facilities, and we would like to thank Antonio Aguilar for assistance in using beamline BM30 B. Publisher Copyright: © 2018 American Chemical Society.

PY - 2018/4/6

Y1 - 2018/4/6

N2 - A well-defined silica-supported monoalkylated tungsten dioxo complex [(Si-O-)W(=O)2(CH2-tBu)] was prepared by treatment of highly dehydroxylated silica (SiO2-700: silica treated at 700 °C under high vacuum) with an ionic precursor complex [NEt4][W(=O)3(CH2-tBu)]. The identity of the resulting neutral monoalkylated tungsten dioxo surface complex was established by means of elemental microanalysis and spectroscopic studies (IR, solid-state NMR, Raman, and X-ray absorption spectroscopies). The supported tungsten complex was found to act as a precatalyst for the self-metathesis of 1-octene in a batch reactor. The mechanistic implications of this reaction are discussed with the support of DFT calculations highlighting the potential occurrence of thus-far unexplored mechanistic pathways.

AB - A well-defined silica-supported monoalkylated tungsten dioxo complex [(Si-O-)W(=O)2(CH2-tBu)] was prepared by treatment of highly dehydroxylated silica (SiO2-700: silica treated at 700 °C under high vacuum) with an ionic precursor complex [NEt4][W(=O)3(CH2-tBu)]. The identity of the resulting neutral monoalkylated tungsten dioxo surface complex was established by means of elemental microanalysis and spectroscopic studies (IR, solid-state NMR, Raman, and X-ray absorption spectroscopies). The supported tungsten complex was found to act as a precatalyst for the self-metathesis of 1-octene in a batch reactor. The mechanistic implications of this reaction are discussed with the support of DFT calculations highlighting the potential occurrence of thus-far unexplored mechanistic pathways.

KW - Olefin metathesis

KW - mechanistic study

KW - metallacyclobutane intermediate

KW - tungsten alkylidene

KW - tungsten dioxo complex

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DO - 10.1021/acscatal.7b04304

M3 - Article

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JF - ACS Catalysis

IS - 4

ER -

A Silica-Supported Monoalkylated Tungsten Dioxo Complex Catalyst for Olefin Metathesis

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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