Skip to content

Research at St Andrews

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

Research output: Contribution to journalArticle

DOI

Open Access permissions

Open

Author(s)

Sai V. C. Vummaleti, David James Nelson, Albert Poater, Adrian Gomez Suarez, David Bradford Cordes, Alexandra Martha Zoya Slawin, Steven Patrick Nolan, Luigi Cavallo

School/Research organisations

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.

Close

Details

Original languageEnglish
Pages (from-to)1895-1904
Number of pages10
JournalChemical Science
Volume6
Issue number3
Early online date2 Jan 2015
DOIs
Publication statusPublished - Mar 2015

Discover related content
Find related publications, people, projects and more using interactive charts.

View graph of relations

Related by author

  1. A facile synthesis of Robinson’s NHC-stabilised diborane(4)

    Trose, M., Cordes, D. B., Slawin, A. M. Z. & Stasch, A., 27 Oct 2020, In : European Journal of Inorganic Chemistry. 2020, 40, p. 3811-3814 5 p.

    Research output: Contribution to journalArticle

  2. Janus face all-cis 1,2,4,5-tetrakis(trifluoromethyl)- and all-cis 1,2,3,4,5,6-hexakis(trifluoromethyl)- cyclohexanes

    Yu, C., Kütt, A., Röschenthaler, G-V., Lebl, T., Cordes, D. B., Slawin, A. M. Z., Buehl, M. & O'Hagan, D., 26 Oct 2020, In : Angewandte Chemie International Edition. 59, 45, p. 19905-19909 6 p.

    Research output: Contribution to journalArticle

  3. Efficient sky-blue organic light-emitting diodes using a highly horizontally oriented thermally activated delayed fluorescence emitter

    Zhang, Z., Crovini, E., dos Santos, P. L., Naqvi, B. A., Cordes, D. B., Slawin, A. M. Z., Sahay, P., Brütting, W., Samuel, I. D. W., Bräse, S. & Zysman-Colman, E., 23 Oct 2020, In : Advanced Optical Materials. Early View, 8 p.

    Research output: Contribution to journalArticle

  4. Structural variations in manganese halide chain compounds mediated by methylimidazolium isomers

    Han, C., Cordes, D. B., Slawin, A. M. Z. & Lightfoot, P., 13 Oct 2020, In : Crystals. 10, 10, 10 p., 930.

    Research output: Contribution to journalArticle

  5. Fast delayed emission in new pyridazine-based compounds

    Krotkus, S., Matulaitis, T., Diesing, S., Copley, G. J., Archer, E., Keum, C., Cordes, D. B., Slawin, A. M. Z., Gather, M. C., Zysman-Colman, E. & Samuel, I. D. W., 13 Oct 2020, (Accepted/In press) In : Frontiers in Chemistry. In press

    Research output: Contribution to journalArticle

Related by journal

  1. Mechanomechanically assisted hydrolysis in the ADOR process

    Rainer, D. N., Rice, C. M., Warrender, S. J., Ashbrook, S. E. & Morris, R. E., 15 Jun 2020, In : Chemical Science. Advance Article, 10 p.

    Research output: Contribution to journalArticle

  2. Method for accurate experimental determination of singlet and triplet exciton diffusion between thermally activated delayed fluorescence molecules

    Jakoby, M., Heidrich, S., Graf von Reventlow, L., Degitz, C., Madayanad Suresh, S., Zysman-Colman, E., Wenzel, W., Richards, B. & Howard, I., 16 Nov 2020, In : Chemical Science. Advance article

    Research output: Contribution to journalArticle

  3. Programmable dynamic covalent nanoparticle building blocks with complementary reactivity

    Marro, N., della Sala, F. & Kay, E. R., 14 Jan 2020, In : Chemical Science. 11, 2, p. 372-383 12 p.

    Research output: Contribution to journalArticle

  4. Tandem sequential catalytic enantioselective synthesis of highly-functionalised tetrahydroindolizine derivatives

    Zhang, S., Greenhalgh, M. D., Slawin, A. M. Z. & Smith, A. D., 12 Mar 2020, In : Chemical Science. Advance Article, 8 p.

    Research output: Contribution to journalArticle

  5. ThX-a next-generation probe for the early detection of amyloid aggregates

    Needham, L. M., Weber, J., Varela, J. A., Fyfe, J. W. B., Do, D. T., Xu, C. K., Tutton, L., Cliffe, R., Keenlyside, B., Klenerman, D., Dobson, C. M., Hunter, C. A., Müller, K. H., O'Holleran, K., Bohndiek, S. E., Snaddon, T. N. & Lee, S. F., 14 May 2020, In : Chemical Science. 11, 18, p. 4578-4583 6 p.

    Research output: Contribution to journalArticle

ID: 161275645

Top