The activation mechanism of Ru-indenylidene complexes in olefin metathesis

César A. Urbina-Blanco; Albert Poater; Tomáš Lébl; Simone Manzini; Alexandra M. Z. Slawin; Luigi Cavallo; Steven P. Nolan

doi:10.1021/ja402700p

The activation mechanism of Ru-indenylidene complexes in olefin metathesis

César A. Urbina-Blanco, Albert Poater, Tomáš Lébl, Simone Manzini, Alexandra M. Z. Slawin, Luigi Cavallo, Steven P. Nolan

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

98 Scopus citations

Abstract

Olefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations. © 2013 American Chemical Society.

Original language	English (US)
Pages (from-to)	7073-7079
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	135
Issue number	18
DOIs	https://doi.org/10.1021/ja402700p
State	Published - Apr 25 2013

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007-2013) under grant agreement no CP-FP 211468-2 EUMET. SPN is a Royal Society Wolfson Research Merit Award holder. LC thanks BSC (QCM-2010-2-0020), and the HPC team of Enea for using the ENEA-GRID and the HPC facilities CRESCO in Portici (Italy) for access to remarkable computational resources. AP thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226), Generalitat de Catalunya (2012BE100824) and European Commission for a Career Integration Grant (CIG09-GA-2011-293900). Dr Julie Broggi is greatly acknowledged for preliminary research leading to this publication, Dr David J. Nelson and Prof. Fernando Febres Cordero are greatly acknowledged for helpful discussions. Umicore is greatly acknowledged for their generous donation of materials.

ASJC Scopus subject areas

Biochemistry
Colloid and Surface Chemistry
General Chemistry
Catalysis

Access to Document

10.1021/ja402700p

Cite this

@article{326d6bd1d5fe45acb9e5eed596f7de47,

title = "The activation mechanism of Ru-indenylidene complexes in olefin metathesis",

abstract = "Olefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations. {\textcopyright} 2013 American Chemical Society.",

author = "Urbina-Blanco, {C{\'e}sar A.} and Albert Poater and Tom{\'a}{\v s} L{\'e}bl and Simone Manzini and Slawin, {Alexandra M. Z.} and Luigi Cavallo and Nolan, {Steven P.}",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007-2013) under grant agreement no CP-FP 211468-2 EUMET. SPN is a Royal Society Wolfson Research Merit Award holder. LC thanks BSC (QCM-2010-2-0020), and the HPC team of Enea for using the ENEA-GRID and the HPC facilities CRESCO in Portici (Italy) for access to remarkable computational resources. AP thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226), Generalitat de Catalunya (2012BE100824) and European Commission for a Career Integration Grant (CIG09-GA-2011-293900). Dr Julie Broggi is greatly acknowledged for preliminary research leading to this publication, Dr David J. Nelson and Prof. Fernando Febres Cordero are greatly acknowledged for helpful discussions. Umicore is greatly acknowledged for their generous donation of materials.",

year = "2013",

month = apr,

day = "25",

doi = "10.1021/ja402700p",

language = "English (US)",

volume = "135",

pages = "7073--7079",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "18",

}

TY - JOUR

T1 - The activation mechanism of Ru-indenylidene complexes in olefin metathesis

AU - Urbina-Blanco, César A.

AU - Poater, Albert

AU - Lébl, Tomáš

AU - Manzini, Simone

AU - Slawin, Alexandra M. Z.

AU - Cavallo, Luigi

AU - Nolan, Steven P.

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007-2013) under grant agreement no CP-FP 211468-2 EUMET. SPN is a Royal Society Wolfson Research Merit Award holder. LC thanks BSC (QCM-2010-2-0020), and the HPC team of Enea for using the ENEA-GRID and the HPC facilities CRESCO in Portici (Italy) for access to remarkable computational resources. AP thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226), Generalitat de Catalunya (2012BE100824) and European Commission for a Career Integration Grant (CIG09-GA-2011-293900). Dr Julie Broggi is greatly acknowledged for preliminary research leading to this publication, Dr David J. Nelson and Prof. Fernando Febres Cordero are greatly acknowledged for helpful discussions. Umicore is greatly acknowledged for their generous donation of materials.

PY - 2013/4/25

Y1 - 2013/4/25

N2 - Olefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations. © 2013 American Chemical Society.

AB - Olefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations. © 2013 American Chemical Society.

UR - http://hdl.handle.net/10754/562761

UR - https://pubs.acs.org/doi/10.1021/ja402700p

UR - http://www.scopus.com/inward/record.url?scp=84877266561&partnerID=8YFLogxK

U2 - 10.1021/ja402700p

DO - 10.1021/ja402700p

M3 - Article

C2 - 23617632

SN - 0002-7863

VL - 135

SP - 7073

EP - 7079

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 18

ER -

The activation mechanism of Ru-indenylidene complexes in olefin metathesis

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

CCDC 887968: Experimental Crystal Structure Determination : Dichloro-bis(tricyclohexylphosphine)-(3-phenylindenylidene)-ruthenium tetrahydrofuran solvate

CCDC 887969: Experimental Crystal Structure Determination : Dichloro-(1,3-dimesitylimidazolidin-2-ylidene)-(3-phenylindenylidene)-triphenylphosphine-ruthenium methanol solvate

Cite this

The activation mechanism of Ru-indenylidene complexes in olefin metathesis

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 887968: Experimental Crystal Structure Determination : Dichloro-bis(tricyclohexylphosphine)-(3-phenylindenylidene)-ruthenium tetrahydrofuran solvate

CCDC 887969: Experimental Crystal Structure Determination : Dichloro-(1,3-dimesitylimidazolidin-2-ylidene)-(3-phenylindenylidene)-triphenylphosphine-ruthenium methanol solvate

Cite this