Variation of the Sterical Properties of the N-Heterocyclic Carbene Coligand in Thermally Triggerable Ruthenium-Based Olefin Metathesis Precatalysts/Initiators

Handle URI:
http://hdl.handle.net/10754/622493
Title:
Variation of the Sterical Properties of the N-Heterocyclic Carbene Coligand in Thermally Triggerable Ruthenium-Based Olefin Metathesis Precatalysts/Initiators
Authors:
Pump, Eva; Leitgeb, Anita; Kozłowska, Anna; Torvisco, Ana; Falivene, Laura ( 0000-0003-1509-6191 ) ; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Grela, Karol; Slugovc, Christian
Abstract:
A series of ruthenium complexes based on the κ(C,N)-(2-(benzo[h]quinolin-10-yl)methylidene ruthenium dichloride fragment featuring different neutral coligands L (L = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene (SIPr), 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene (SIMes), 1,3-bis(2,4-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene (SIXyl), and 1,3-bis(2-methylphenyl)-4,5-dihydroimidazol-2-ylidene (SITol)) was prepared, characterized, and tested in the thermally induced ring-opening metathesis polymerization of dicyclopentadiene. In addition, the corresponding tricyclohexylphosphine derivative was investigated for comparison. All compounds were isolated as their trans-dichloro isomers. NMR spectroscopic features as well as structural features are, particularly within the NHC-bearing complexes, very similar, but their polymerization activity at elevated temperatures is distinctly different. While the SIMes derivative shows the desired properties, i.e., latency at room temperature and pronounced polymerization activity at elevated temperature, all other preinitiators do not. The preinitiator featuring the SIPr coligand is the most latent one, needing temperatures > 140 °C to show moderate activity in the polymerization of dicyclopentadiene. Compounds bearing the smaller N-heterocyclic carbene congeners are stable and latent at room temperature, but decompose upon heating, diminishing the polymerization activity at elevated temperatures. Density functional calculations show that the SIMes derivative is the easiest to activate and yields the most stable 14-electron intermediate. Finally calculations reveal a distinct influence of the nature of the N-heterocyclic carbene ligand on the position of the equilibrium of cis- and trans-dichloro isomers of the complexes. While the SIPr and the SIMes derivatives prefer the cis-configuration, all other derivatives favor, at least in solvents with low dielectric constants, the trans-configuration. These computational findings were supported by the isolation and full characterization of the cis-dichloro isomer of the SIMes-bearing preinitiator obtained upon heating of its trans-isomer at 140 °C.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Pump E, Leitgeb A, Kozłowska A, Torvisco A, Falivene L, et al. (2015) Variation of the Sterical Properties of the N-Heterocyclic Carbene Coligand in Thermally Triggerable Ruthenium-Based Olefin Metathesis Precatalysts/Initiators. Organometallics 34: 5383–5392. Available: http://dx.doi.org/10.1021/acs.organomet.5b00715.
Publisher:
American Chemical Society (ACS)
Journal:
Organometallics
Issue Date:
9-Nov-2015
DOI:
10.1021/acs.organomet.5b00715
Type:
Article
ISSN:
0276-7333; 1520-6041
Sponsors:
Authors acknowledge the OeAD for the WTZ PL10/2014 exchange grant. 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). L.C. thanks the King Abdullah University of Science and Technology for supporting this research. The Polish authors thank the Foundation for Polish Science for the "Team"-program cofinanced by the European Regional Development Fund Operational Program Innovative Economy 2007/2013.
Is Supplemented By:
Pump, E., Leitgeb, A., Kozłowska, A., Torvisco, A., Falivene, L., Cavallo, L., … Slugovc, C. (2015). CCDC 1419405: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jn08g; DOI:10.5517/cc1jn08g; HANDLE:http://hdl.handle.net/10754/624458; Pump, E., Leitgeb, A., Kozłowska, A., Torvisco, A., Falivene, L., Cavallo, L., … Slugovc, C. (2015). CCDC 1419406: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jn09h; DOI:10.5517/cc1jn09h; HANDLE:http://hdl.handle.net/10754/624459; Pump, E., Leitgeb, A., Kozłowska, A., Torvisco, A., Falivene, L., Cavallo, L., … Slugovc, C. (2015). CCDC 1419407: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jn0bj; DOI:10.5517/cc1jn0bj; HANDLE:http://hdl.handle.net/10754/624460; Pump, E., Leitgeb, A., Kozłowska, A., Torvisco, A., Falivene, L., Cavallo, L., … Slugovc, C. (2015). CCDC 1419408: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jn0ck; DOI:10.5517/cc1jn0ck; HANDLE:http://hdl.handle.net/10754/624461; Pump, E., Leitgeb, A., Kozłowska, A., Torvisco, A., Falivene, L., Cavallo, L., … Slugovc, C. (2015). CCDC 1419409: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jn0dl; DOI:10.5517/cc1jn0dl; HANDLE:http://hdl.handle.net/10754/624462
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorPump, Evaen
dc.contributor.authorLeitgeb, Anitaen
dc.contributor.authorKozłowska, Annaen
dc.contributor.authorTorvisco, Anaen
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorGrela, Karolen
dc.contributor.authorSlugovc, Christianen
dc.date.accessioned2017-01-02T09:28:34Z-
dc.date.available2017-01-02T09:28:34Z-
dc.date.issued2015-11-09en
dc.identifier.citationPump E, Leitgeb A, Kozłowska A, Torvisco A, Falivene L, et al. (2015) Variation of the Sterical Properties of the N-Heterocyclic Carbene Coligand in Thermally Triggerable Ruthenium-Based Olefin Metathesis Precatalysts/Initiators. Organometallics 34: 5383–5392. Available: http://dx.doi.org/10.1021/acs.organomet.5b00715.en
dc.identifier.issn0276-7333en
dc.identifier.issn1520-6041en
dc.identifier.doi10.1021/acs.organomet.5b00715en
dc.identifier.urihttp://hdl.handle.net/10754/622493-
dc.description.abstractA series of ruthenium complexes based on the κ(C,N)-(2-(benzo[h]quinolin-10-yl)methylidene ruthenium dichloride fragment featuring different neutral coligands L (L = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene (SIPr), 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene (SIMes), 1,3-bis(2,4-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene (SIXyl), and 1,3-bis(2-methylphenyl)-4,5-dihydroimidazol-2-ylidene (SITol)) was prepared, characterized, and tested in the thermally induced ring-opening metathesis polymerization of dicyclopentadiene. In addition, the corresponding tricyclohexylphosphine derivative was investigated for comparison. All compounds were isolated as their trans-dichloro isomers. NMR spectroscopic features as well as structural features are, particularly within the NHC-bearing complexes, very similar, but their polymerization activity at elevated temperatures is distinctly different. While the SIMes derivative shows the desired properties, i.e., latency at room temperature and pronounced polymerization activity at elevated temperature, all other preinitiators do not. The preinitiator featuring the SIPr coligand is the most latent one, needing temperatures > 140 °C to show moderate activity in the polymerization of dicyclopentadiene. Compounds bearing the smaller N-heterocyclic carbene congeners are stable and latent at room temperature, but decompose upon heating, diminishing the polymerization activity at elevated temperatures. Density functional calculations show that the SIMes derivative is the easiest to activate and yields the most stable 14-electron intermediate. Finally calculations reveal a distinct influence of the nature of the N-heterocyclic carbene ligand on the position of the equilibrium of cis- and trans-dichloro isomers of the complexes. While the SIPr and the SIMes derivatives prefer the cis-configuration, all other derivatives favor, at least in solvents with low dielectric constants, the trans-configuration. These computational findings were supported by the isolation and full characterization of the cis-dichloro isomer of the SIMes-bearing preinitiator obtained upon heating of its trans-isomer at 140 °C.en
dc.description.sponsorshipAuthors acknowledge the OeAD for the WTZ PL10/2014 exchange grant. 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). L.C. thanks the King Abdullah University of Science and Technology for supporting this research. The Polish authors thank the Foundation for Polish Science for the "Team"-program cofinanced by the European Regional Development Fund Operational Program Innovative Economy 2007/2013.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleVariation of the Sterical Properties of the N-Heterocyclic Carbene Coligand in Thermally Triggerable Ruthenium-Based Olefin Metathesis Precatalysts/Initiatorsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalOrganometallicsen
dc.contributor.institutionInstitute for Chemistry and Technology of Materials, Graz University of Technology, NAWI Graz, Stremayrgasse 9, Graz, A 8010, Austriaen
dc.contributor.institutionBiological and Chemical Research Center, Department of Chemistry, University of Warsaw, Zwirki i Wigury 101, Warszawa, 02-089, Polanden
dc.contributor.institutionInstitute of Inorganic Chemistry, Graz University of Technology, NAWI Graz, Stremayrgasse 9, Graz, A 8010, Austriaen
kaust.authorFalivene, Lauraen
kaust.authorCavallo, Luigien
dc.relation.isSupplementedByPump, E., Leitgeb, A., Kozłowska, A., Torvisco, A., Falivene, L., Cavallo, L., … Slugovc, C. (2015). CCDC 1419405: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jn08gen
dc.relation.isSupplementedByDOI:10.5517/cc1jn08gen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624458en
dc.relation.isSupplementedByPump, E., Leitgeb, A., Kozłowska, A., Torvisco, A., Falivene, L., Cavallo, L., … Slugovc, C. (2015). CCDC 1419406: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jn09hen
dc.relation.isSupplementedByDOI:10.5517/cc1jn09hen
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dc.relation.isSupplementedByPump, E., Leitgeb, A., Kozłowska, A., Torvisco, A., Falivene, L., Cavallo, L., … Slugovc, C. (2015). CCDC 1419407: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jn0bjen
dc.relation.isSupplementedByDOI:10.5517/cc1jn0bjen
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dc.relation.isSupplementedByPump, E., Leitgeb, A., Kozłowska, A., Torvisco, A., Falivene, L., Cavallo, L., … Slugovc, C. (2015). CCDC 1419408: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jn0cken
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dc.relation.isSupplementedByPump, E., Leitgeb, A., Kozłowska, A., Torvisco, A., Falivene, L., Cavallo, L., … Slugovc, C. (2015). CCDC 1419409: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jn0dlen
dc.relation.isSupplementedByDOI:10.5517/cc1jn0dlen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624462en
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