Grafting mechanism and olefin metathesis activity of well-defined silica-supported Mo imido alkyl alkylidene complexes

Frédéric Blanc; Alain Salameh; Jean Thivolle-Cazat; Jean Marie Basset; Christophe Copéret; Amritanshu Sinha; Richard R. Schrock

doi:10.1016/j.crci.2007.02.017

Grafting mechanism and olefin metathesis activity of well-defined silica-supported Mo imido alkyl alkylidene complexes

Frédéric Blanc, Alain Salameh, Jean Thivolle-Cazat, Jean Marie Basset, Christophe Copéret^*, Amritanshu Sinha, Richard R. Schrock

^*Corresponding author for this work

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

25 Scopus citations

Abstract

Grafting of [Mo(NAr)({double bond, long}CHCMe₂R)(CH₂tBu)₂], 1-R (R = Me or Ph) on the surface silanols of SiO_2-(700) gives 2-R through the electrophilic cleavage of the Mo-C σ-bond according to labelling (GC/MS and solid-state NMR) and reactivity studies (monitoring initiation). Similarly, molecular silanol derivatives react with 1-Ph also to give directly the monosiloxy derivatives. Therefore, surface or molecular silanols have reactivities similar to alcohols and phenols having pK_a ≥ 9. Finally, the surface complex 2-R (R = Me or Ph) is a highly efficient olefin metathesis catalyst.

Original language	English (US)
Pages (from-to)	137-146
Number of pages	10
Journal	Comptes Rendus Chimie
Volume	11
Issue number	1-2
DOIs	https://doi.org/10.1016/j.crci.2007.02.017
State	Published - Jan 2008
Externally published	Yes

Bibliographical note

Funding Information:
F.B. is grateful to the French Ministry of Education, Research and Technology (MENRT) for a graduate fellowship. A.S. thanks BASF AG for a graduate student fellowship. The authors thank N. Legagneux, A. Puissegur and L. Weinberg (CPE project students) for their participation in part of this work. We are indebted to the CNRS, ANR (ANR JC05_46372), ESCPE Lyon and the National Science Foundation for financial supports.

Keywords

Heterogeneous catalysis
Mo imido alkylidene
Olefin metathesis
Silica
Surface organometallic chemistry

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering

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10.1016/j.crci.2007.02.017

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title = "Grafting mechanism and olefin metathesis activity of well-defined silica-supported Mo imido alkyl alkylidene complexes",

abstract = "Grafting of [Mo(NAr)({double bond, long}CHCMe2R)(CH2tBu)2], 1-R (R = Me or Ph) on the surface silanols of SiO2-(700) gives 2-R through the electrophilic cleavage of the Mo-C σ-bond according to labelling (GC/MS and solid-state NMR) and reactivity studies (monitoring initiation). Similarly, molecular silanol derivatives react with 1-Ph also to give directly the monosiloxy derivatives. Therefore, surface or molecular silanols have reactivities similar to alcohols and phenols having pKa ≥ 9. Finally, the surface complex 2-R (R = Me or Ph) is a highly efficient olefin metathesis catalyst.",

keywords = "Heterogeneous catalysis, Mo imido alkylidene, Olefin metathesis, Silica, Surface organometallic chemistry",

author = "Fr{\'e}d{\'e}ric Blanc and Alain Salameh and Jean Thivolle-Cazat and Basset, {Jean Marie} and Christophe Cop{\'e}ret and Amritanshu Sinha and Schrock, {Richard R.}",

note = "Funding Information: F.B. is grateful to the French Ministry of Education, Research and Technology (MENRT) for a graduate fellowship. A.S. thanks BASF AG for a graduate student fellowship. The authors thank N. Legagneux, A. Puissegur and L. Weinberg (CPE project students) for their participation in part of this work. We are indebted to the CNRS, ANR (ANR JC05_46372), ESCPE Lyon and the National Science Foundation for financial supports.",

year = "2008",

month = jan,

doi = "10.1016/j.crci.2007.02.017",

language = "English (US)",

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pages = "137--146",

journal = "Comptes Rendus Chimie",

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AU - Blanc, Frédéric

AU - Salameh, Alain

AU - Thivolle-Cazat, Jean

AU - Basset, Jean Marie

AU - Copéret, Christophe

AU - Sinha, Amritanshu

AU - Schrock, Richard R.

N1 - Funding Information: F.B. is grateful to the French Ministry of Education, Research and Technology (MENRT) for a graduate fellowship. A.S. thanks BASF AG for a graduate student fellowship. The authors thank N. Legagneux, A. Puissegur and L. Weinberg (CPE project students) for their participation in part of this work. We are indebted to the CNRS, ANR (ANR JC05_46372), ESCPE Lyon and the National Science Foundation for financial supports.

PY - 2008/1

Y1 - 2008/1

N2 - Grafting of [Mo(NAr)({double bond, long}CHCMe2R)(CH2tBu)2], 1-R (R = Me or Ph) on the surface silanols of SiO2-(700) gives 2-R through the electrophilic cleavage of the Mo-C σ-bond according to labelling (GC/MS and solid-state NMR) and reactivity studies (monitoring initiation). Similarly, molecular silanol derivatives react with 1-Ph also to give directly the monosiloxy derivatives. Therefore, surface or molecular silanols have reactivities similar to alcohols and phenols having pKa ≥ 9. Finally, the surface complex 2-R (R = Me or Ph) is a highly efficient olefin metathesis catalyst.

AB - Grafting of [Mo(NAr)({double bond, long}CHCMe2R)(CH2tBu)2], 1-R (R = Me or Ph) on the surface silanols of SiO2-(700) gives 2-R through the electrophilic cleavage of the Mo-C σ-bond according to labelling (GC/MS and solid-state NMR) and reactivity studies (monitoring initiation). Similarly, molecular silanol derivatives react with 1-Ph also to give directly the monosiloxy derivatives. Therefore, surface or molecular silanols have reactivities similar to alcohols and phenols having pKa ≥ 9. Finally, the surface complex 2-R (R = Me or Ph) is a highly efficient olefin metathesis catalyst.

KW - Heterogeneous catalysis

KW - Mo imido alkylidene

KW - Olefin metathesis

KW - Silica

KW - Surface organometallic chemistry

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Grafting mechanism and olefin metathesis activity of well-defined silica-supported Mo imido alkyl alkylidene complexes

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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