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 journalArticlepeer-review

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. Solvothermal synthesis of a novel calcium metal-organic 2 framework: high temperature and electrochemical behaviour

    Main, R. M., Cordes, D. B., Desai, A. V., Slawin, A. M. Z., Wheatley, P., Armstrong, A. R. & Morris, R. E., 22 Nov 2021, In: Molecules. 26, 22, 7048.

    Research output: Contribution to journalArticlepeer-review

  2. Janus all-cis 2,3,4,5,6-pentafluorocyclohexyl building blocks applied to medicinal chemistry and bioactives discovery chemistry

    Clark, J., Neyyappadath, R. M., Yu, C., Slawin, A. M. Z., Cordes, D. B. & O'Hagan, D., 17 Nov 2021, In: Chemistry - A European Journal. 27, 64, p. 16000-16005 7 p., 202102819.

    Research output: Contribution to journalArticlepeer-review

  3. Scope, limitations and mechanistic analysis of the HyperBTM-catalyzed acylative kinetic resolution of tertiary heterocyclic alcohols

    Smith, S., Greenhalgh, M. D., Feoktistova, T., Walden, D. M., Taylor, J. E., Cordes, D. B., Slawin, A. M. Z., Cheong, P. H-Y. & Smith, A. D., 11 Nov 2021, (E-pub ahead of print) In: European Journal of Organic Chemistry. Early View

    Research output: Contribution to journalArticlepeer-review

  4. Simple and inexpensive method for the detection of carbon monoxide released from thermal cheletropic decarbonylation reactions

    Smellie, I., Carpenter-Warren, C. L., Chalmers, B. A., Cordes, D. B., Freire De Araujo Gouy, R. P., Keddie, N. S., Lebl, T., Patterson, I. L. J. & Slawin, A. M. Z., 9 Nov 2021, In: Journal of Chemical Education. 98, 11, p. 3608-3613

    Research output: Contribution to journalArticlepeer-review

  5. Substitution effects on a new pyridylbenzimidazole acceptor for thermally activated delayed fluorescence and their use in organic light-emitting diodes

    Hall, D., Rajamalli, P., Duda, E., Madayanad Suresh, S., Rodella, F., Bagnich, S., Carpenter-Warren, C. L., Cordes, D. B., Slawin, A. M. Z., Strohriegl, P., Beljonne, D., Köhler, A., Olivier, Y. & Zysman-Colman, E., 18 Oct 2021, In: Advanced Optical Materials. 9, 20, 13 p., 2100846.

    Research output: Contribution to journalArticlepeer-review

Related by journal

  1. Catalytic enantioselective synthesis of 1,4-dihydropyridines via the addition of C(1)-ammonium enolates to pyridinium salts

    McLaughlin, C., Bitai, J., Barber, L., Slawin, A. & Smith, A. D., 6 Aug 2021, (E-pub ahead of print) In: Chemical Science. Advance Article, 11 p.

    Research output: Contribution to journalArticlepeer-review

  2. Supramolecular packing of alkyl substituted Janus face all-cis 2,3,4,5,6-pentafluorocyclohexyl motifs

    Clark, J., Taylor, A., Geddis, A., Neyyappadath, R. M., Piscelli, B., Yu, C., Cordes, D. B., Slawin, A. M. Z., Cormanich, R., Guldin, S. & O'Hagan, D., 4 Jun 2021, (E-pub ahead of print) In: Chemical Science. Advance Article, 8 p.

    Research output: Contribution to journalArticlepeer-review

  3. Albumin-mediated alteration of plasma zinc speciation by fatty acids modulates blood clotting in type-2 diabetes

    Sobczak, A. I. S., Katundu, K. G. H., Phoenix, F. A., Khazaipoul, S., Yu, R., Lampiao, F., Stefanowicz, F., Blindauer, C. A., Pitt, S. J., Smith, T. K., Ajjan, R. A. & Stewart, A. J., 21 Mar 2021, In: Chemical Science. 12, 11, p. 4079-4093 15 p.

    Research output: Contribution to journalArticlepeer-review

  4. 17O NMR spectroscopy of crystalline microporous materials

    Ashbrook, S. E., Davis, Z., Morris, R. & Rice, C. M., 25 Feb 2021, (E-pub ahead of print) In: Chemical Science. Advance Article, 21 p.

    Research output: Contribution to journalReview articlepeer-review

  5. Single-step synthesis and interface tuning of core–shell metal–organic framework nanoparticles

    Orr, K. W. P., Collins, S. M., Reynolds, E. M., Nightingale, F., Boström, H. L. B., Cassidy, S. J., Dawson, D. M., Ashbrook, S. E., Magdysyuk, O. V., Midgley, P., Goodwin, A. L. & Yeung, H. H-M., 9 Feb 2021, (E-pub ahead of print) In: Chemical Science. Advance Article, 9 p.

    Research output: Contribution to journalArticlepeer-review

ID: 161275645

Top