What can NMR spectroscopy of selenoureas and phosphinidenes teach us about the π-accepting abilities of N-heterocyclic carbenes?

Handle URI:
http://hdl.handle.net/10754/550524
Title:
What can NMR spectroscopy of selenoureas and phosphinidenes teach us about the π-accepting abilities of N-heterocyclic carbenes?
Authors:
Vummaleti, Sai V. C. ( 0000-0001-7276-2475 ) ; Nelson, David J.; Poater, Albert; Gómez-Suárez, Adrián; Cordes, David B.; Slawin, Alexandra M. Z.; Nolan, Steven P.; Cavallo, Luigi ( 0000-0002-1398-338X )
Abstract:
The electronic nature of the interaction of NHCs with metal centres is of interest when exploring their properties, how these properties influence those of metal complexes, and how these properties might depend on ligand structure. Selenourea and phosphinidene complexes have been proposed to allow the measurement of the π-accepting ability of NHCs, independent of their σ-donating ability, via the collection of 77Se or 31P NMR spectra, respectively. Herein, the synthesis and characterisation of selenoureas derived from a range of imidazol-2-ylidenes, 4,5-dihydroimidazol-2-ylidenes and triazol-2-ylidenes are documented. Computational studies are used to explore the link between the shielding of the selenium centre and the electronic properties of the NHCs. Results show that δSe is correlated to the energy gap between a filled lone pair orbital on Se and the empty π* orbital corresponding to the Se–NHC bond. Bond energy decomposition analysis indicated no correlation between the orbital σ-contribution to bonding and the chemical shielding, while a good correlation was found between the π-contribution to bonding and the chemical shielding, confirming that this technique is indeed able to quantify the ability of NHCs to accept π-electron density. Calculations conducted on phosphinidene adducts yielded similar results. With the link between δSe and δP and π-back bonding ability clearly established, these compounds represent useful ways in which to fully understand and quantify this aspect of the electronic properties of NHCs.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
What can NMR spectroscopy of selenoureas and phosphinidenes teach us about the π-accepting abilities of N-heterocyclic carbenes? 2015, 6 (3):1895 Chem. Sci.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Chem. Sci.
Issue Date:
2-Jan-2015
DOI:
10.1039/C4SC03264K
Type:
Article
ISSN:
2041-6520; 2041-6539
Is Supplemented By:
Vummaleti, S. V. C., Nelson, D. J., Poater, A., Gómez-Suárez, A., Cordes, D. B., Slawin, A. M. Z., … Cavallo, L. (2015). CCDC 1024807: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc13dd96; DOI:10.5517/cc13dd96; HANDLE:http://hdl.handle.net/10754/624360; Vummaleti, S. V. C., Nelson, D. J., Poater, A., Gómez-Suárez, A., Cordes, D. B., Slawin, A. M. Z., … Cavallo, L. (2015). CCDC 1024808: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc13ddb7; DOI:10.5517/cc13ddb7; HANDLE:http://hdl.handle.net/10754/624361; Vummaleti, S. V. C., Nelson, D. J., Poater, A., Gómez-Suárez, A., Cordes, D. B., Slawin, A. M. Z., … Cavallo, L. (2015). CCDC 1024809: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc13ddc8; DOI:10.5517/cc13ddc8; HANDLE:http://hdl.handle.net/10754/624362; Vummaleti, S. V. C., Nelson, D. J., Poater, A., Gómez-Suárez, A., Cordes, D. B., Slawin, A. M. Z., … Cavallo, L. (2015). CCDC 1024810: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc13ddd9; DOI:10.5517/cc13ddd9; HANDLE:http://hdl.handle.net/10754/624363; Vummaleti, S. V. C., Nelson, D. J., Poater, A., Gómez-Suárez, A., Cordes, D. B., Slawin, A. M. Z., … Cavallo, L. (2015). CCDC 1024811: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc13ddfb; DOI:10.5517/cc13ddfb; HANDLE:http://hdl.handle.net/10754/624364; Vummaleti, S. V. C., Nelson, D. J., Poater, A., Gómez-Suárez, A., Cordes, D. B., Slawin, A. M. Z., … Cavallo, L. (2015). CCDC 1024812: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc13ddgc; DOI:10.5517/cc13ddgc; HANDLE:http://hdl.handle.net/10754/624365; Vummaleti, S. V. C., Nelson, D. J., Poater, A., Gómez-Suárez, A., Cordes, D. B., Slawin, A. M. Z., … Cavallo, L. (2015). CCDC 1024813: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc13ddhd; DOI:10.5517/cc13ddhd; HANDLE:http://hdl.handle.net/10754/624366; Vummaleti, S. V. C., Nelson, D. J., Poater, A., Gómez-Suárez, A., Cordes, D. B., Slawin, A. M. Z., … Cavallo, L. (2015). CCDC 1024814: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc13ddjf; DOI:10.5517/cc13ddjf; HANDLE:http://hdl.handle.net/10754/624367; Vummaleti, S. V. C., Nelson, D. J., Poater, A., Gómez-Suárez, A., Cordes, D. B., Slawin, A. M. Z., … Cavallo, L. (2015). CCDC 1024815: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc13ddkg; DOI:10.5517/cc13ddkg; HANDLE:http://hdl.handle.net/10754/624368; Vummaleti, S. V. C., Nelson, D. J., Poater, A., Gómez-Suárez, A., Cordes, D. B., Slawin, A. M. Z., … Cavallo, L. (2015). CCDC 1024816: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc13ddlh; DOI:10.5517/cc13ddlh; HANDLE:http://hdl.handle.net/10754/624369; Vummaleti, S. V. C., Nelson, D. J., Poater, A., Gómez-Suárez, A., Cordes, D. B., Slawin, A. M. Z., … Cavallo, L. (2015). CCDC 1024817: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc13ddmj; DOI:10.5517/cc13ddmj; HANDLE:http://hdl.handle.net/10754/624370; Vummaleti, S. V. C., Nelson, D. J., Poater, A., Gómez-Suárez, A., Cordes, D. B., Slawin, A. M. Z., … Cavallo, L. (2015). CCDC 1024818: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc13ddnk; DOI:10.5517/cc13ddnk; HANDLE:http://hdl.handle.net/10754/624371
Additional Links:
http://xlink.rsc.org/?DOI=C4SC03264K
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorVummaleti, Sai V. C.en
dc.contributor.authorNelson, David J.en
dc.contributor.authorPoater, Alberten
dc.contributor.authorGómez-Suárez, Adriánen
dc.contributor.authorCordes, David B.en
dc.contributor.authorSlawin, Alexandra M. Z.en
dc.contributor.authorNolan, Steven P.en
dc.contributor.authorCavallo, Luigien
dc.date.accessioned2015-04-23T14:30:27Zen
dc.date.available2015-04-23T14:30:27Zen
dc.date.issued2015-01-02en
dc.identifier.citationWhat can NMR spectroscopy of selenoureas and phosphinidenes teach us about the π-accepting abilities of N-heterocyclic carbenes? 2015, 6 (3):1895 Chem. Sci.en
dc.identifier.issn2041-6520en
dc.identifier.issn2041-6539en
dc.identifier.doi10.1039/C4SC03264Ken
dc.identifier.urihttp://hdl.handle.net/10754/550524en
dc.description.abstractThe electronic nature of the interaction of NHCs with metal centres is of interest when exploring their properties, how these properties influence those of metal complexes, and how these properties might depend on ligand structure. Selenourea and phosphinidene complexes have been proposed to allow the measurement of the π-accepting ability of NHCs, independent of their σ-donating ability, via the collection of 77Se or 31P NMR spectra, respectively. Herein, the synthesis and characterisation of selenoureas derived from a range of imidazol-2-ylidenes, 4,5-dihydroimidazol-2-ylidenes and triazol-2-ylidenes are documented. Computational studies are used to explore the link between the shielding of the selenium centre and the electronic properties of the NHCs. Results show that δSe is correlated to the energy gap between a filled lone pair orbital on Se and the empty π* orbital corresponding to the Se–NHC bond. Bond energy decomposition analysis indicated no correlation between the orbital σ-contribution to bonding and the chemical shielding, while a good correlation was found between the π-contribution to bonding and the chemical shielding, confirming that this technique is indeed able to quantify the ability of NHCs to accept π-electron density. Calculations conducted on phosphinidene adducts yielded similar results. With the link between δSe and δP and π-back bonding ability clearly established, these compounds represent useful ways in which to fully understand and quantify this aspect of the electronic properties of NHCs.en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.urlhttp://xlink.rsc.org/?DOI=C4SC03264Ken
dc.rightsThis article is licensed under a Creative Commons Attribution 3.0 Unported Licence.http://creativecommons.org/licenses/by/3.0/en
dc.titleWhat can NMR spectroscopy of selenoureas and phosphinidenes teach us about the π-accepting abilities of N-heterocyclic carbenes?en
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalChem. Sci.en
dc.eprint.versionPublisher's Version/PDFen
dc.contributor.institutionEaStCHEM School of Chemistry, University of St Andrews, Purdie Building, North Haugh, St Andrews, UKen
dc.contributor.institutionWestCHEM Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, UKen
dc.contributor.institutionInstitut de Química Computacional i Catàlisi and Department de Química, Universitat de Girona, Campus de Motilivi, Girona, Spainen
kaust.authorVummaleti, Sai V. C.en
kaust.authorCavallo, Luigien
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