Impact of electronic modification of the chelating benzylidene ligand in cis-dichloro-configured second-generation olefin metathesis catalysts on their activity

Eva Pump; Albert Poater; Michaela Zirngast; Ana Torvisco; Roland C. Fischer; Luigi Cavallo; Christian Slugovc

doi:10.1021/om500315t

Impact of electronic modification of the chelating benzylidene ligand in cis-dichloro-configured second-generation olefin metathesis catalysts on their activity

Eva Pump, Albert Poater, Michaela Zirngast, Ana Torvisco, Roland C. Fischer, Luigi Cavallo, Christian Slugovc

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

36 Scopus citations

Abstract

A series of electronically modified second-generation cis-dichloro ruthenium ester chelating benzylidene complexes was prepared, characterized, and benchmarked in a typical ring-opening metathesis polymerization (ROMP) experiment. The electronic tuning of the parent chelating benzylidene ligand (2-ethyl ester benzylidene) was achieved by substitution at the 4- and 5-positions with electron-withdrawing nitro or electron-donating methoxy groups. The effect of the electronic tuning on the cis-trans isomerization process was studied experimentally and theoretically. Density functional theory calculations clearly revealed the influence of electronic modification on the relative stability between the cis and trans isomers, which is decisive for the activity of the studied compounds as initiators in ROMP. © 2014 American Chemical Society.

Original language	English (US)
Pages (from-to)	2806-2813
Number of pages	8
Journal	Organometallics
Volume	33
Issue number	11
DOIs	https://doi.org/10.1021/om500315t
State	Published - May 27 2014

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: E.P. gratefully acknowledges the receipt of the "Chemical Monthly Fellowship" financed by Springer Verlag, the Austrian Academy of Sciences (OAW), and the Gesellschaft Osterreichischer Chemiker (GOCH). A.P. thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226) and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900).

ASJC Scopus subject areas

Organic Chemistry
Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/om500315t

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@article{021eec71ff4349a2b9bea8717174cfa3,

title = "Impact of electronic modification of the chelating benzylidene ligand in cis-dichloro-configured second-generation olefin metathesis catalysts on their activity",

abstract = "A series of electronically modified second-generation cis-dichloro ruthenium ester chelating benzylidene complexes was prepared, characterized, and benchmarked in a typical ring-opening metathesis polymerization (ROMP) experiment. The electronic tuning of the parent chelating benzylidene ligand (2-ethyl ester benzylidene) was achieved by substitution at the 4- and 5-positions with electron-withdrawing nitro or electron-donating methoxy groups. The effect of the electronic tuning on the cis-trans isomerization process was studied experimentally and theoretically. Density functional theory calculations clearly revealed the influence of electronic modification on the relative stability between the cis and trans isomers, which is decisive for the activity of the studied compounds as initiators in ROMP. {\textcopyright} 2014 American Chemical Society.",

author = "Eva Pump and Albert Poater and Michaela Zirngast and Ana Torvisco and Fischer, {Roland C.} and Luigi Cavallo and Christian Slugovc",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: E.P. gratefully acknowledges the receipt of the {"}Chemical Monthly Fellowship{"} financed by Springer Verlag, the Austrian Academy of Sciences (OAW), and the Gesellschaft Osterreichischer Chemiker (GOCH). A.P. thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226) and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900).",

year = "2014",

month = may,

day = "27",

doi = "10.1021/om500315t",

language = "English (US)",

volume = "33",

pages = "2806--2813",

journal = "Organometallics",

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publisher = "American Chemical Society",

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T1 - Impact of electronic modification of the chelating benzylidene ligand in cis-dichloro-configured second-generation olefin metathesis catalysts on their activity

AU - Pump, Eva

AU - Poater, Albert

AU - Zirngast, Michaela

AU - Torvisco, Ana

AU - Fischer, Roland C.

AU - Cavallo, Luigi

AU - Slugovc, Christian

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: E.P. gratefully acknowledges the receipt of the "Chemical Monthly Fellowship" financed by Springer Verlag, the Austrian Academy of Sciences (OAW), and the Gesellschaft Osterreichischer Chemiker (GOCH). A.P. thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226) and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900).

PY - 2014/5/27

Y1 - 2014/5/27

N2 - A series of electronically modified second-generation cis-dichloro ruthenium ester chelating benzylidene complexes was prepared, characterized, and benchmarked in a typical ring-opening metathesis polymerization (ROMP) experiment. The electronic tuning of the parent chelating benzylidene ligand (2-ethyl ester benzylidene) was achieved by substitution at the 4- and 5-positions with electron-withdrawing nitro or electron-donating methoxy groups. The effect of the electronic tuning on the cis-trans isomerization process was studied experimentally and theoretically. Density functional theory calculations clearly revealed the influence of electronic modification on the relative stability between the cis and trans isomers, which is decisive for the activity of the studied compounds as initiators in ROMP. © 2014 American Chemical Society.

AB - A series of electronically modified second-generation cis-dichloro ruthenium ester chelating benzylidene complexes was prepared, characterized, and benchmarked in a typical ring-opening metathesis polymerization (ROMP) experiment. The electronic tuning of the parent chelating benzylidene ligand (2-ethyl ester benzylidene) was achieved by substitution at the 4- and 5-positions with electron-withdrawing nitro or electron-donating methoxy groups. The effect of the electronic tuning on the cis-trans isomerization process was studied experimentally and theoretically. Density functional theory calculations clearly revealed the influence of electronic modification on the relative stability between the cis and trans isomers, which is decisive for the activity of the studied compounds as initiators in ROMP. © 2014 American Chemical Society.

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U2 - 10.1021/om500315t

DO - 10.1021/om500315t

M3 - Article

SN - 0276-7333

VL - 33

SP - 2806

EP - 2813

JO - Organometallics

JF - Organometallics

IS - 11

ER -

Impact of electronic modification of the chelating benzylidene ligand in cis-dichloro-configured second-generation olefin metathesis catalysts on their activity

Abstract

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CCDC 977279: Experimental Crystal Structure Determination : dichloro-(1,3-dimesitylimidazolidin-2-ylidene)-(2-(ethoxycarbonyl)-4-nitrobenzylidene)-ruthenium unknown solvate

CCDC 977280: Experimental Crystal Structure Determination : dichloro-(1,3-dimesitylimidazolidin-2-ylidene)-(2-(ethoxycarbonyl)-4-methoxybenzylidene)-ruthenium

CCDC 977278: Experimental Crystal Structure Determination : dichloro-(1,3-dimesitylimidazolidin-2-ylidene)-(2-(ethoxycarbonyl)-5-nitrobenzylidene)-ruthenium

Cite this

Impact of electronic modification of the chelating benzylidene ligand in cis-dichloro-configured second-generation olefin metathesis catalysts on their activity

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 977279: Experimental Crystal Structure Determination : dichloro-(1,3-dimesitylimidazolidin-2-ylidene)-(2-(ethoxycarbonyl)-4-nitrobenzylidene)-ruthenium unknown solvate

CCDC 977280: Experimental Crystal Structure Determination : dichloro-(1,3-dimesitylimidazolidin-2-ylidene)-(2-(ethoxycarbonyl)-4-methoxybenzylidene)-ruthenium

CCDC 977278: Experimental Crystal Structure Determination : dichloro-(1,3-dimesitylimidazolidin-2-ylidene)-(2-(ethoxycarbonyl)-5-nitrobenzylidene)-ruthenium

Cite this