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

Chemistry

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

43 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 (US)
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 - Apr 6 2018

Bibliographical note

Publisher Copyright:
© 2018 American Chemical Society.

Keywords

Olefin metathesis
mechanistic study
metallacyclobutane intermediate
tungsten alkylidene
tungsten dioxo complex

ASJC Scopus subject areas

General Chemistry
Catalysis

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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 = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = apr,

day = "6",

doi = "10.1021/acscatal.7b04304",

language = "English (US)",

volume = "8",

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T1 - A Silica-Supported Monoalkylated Tungsten Dioxo Complex Catalyst for Olefin Metathesis

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

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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SN - 2155-5435

VL - 8

SP - 2715

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JO - ACS Catalysis

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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