Skip to content

Research at St Andrews

Inner-sphere versus outer-sphere coordination of BF4- in a NHC-gold(I) complex

Research output: Research - peer-reviewArticle

DOI

Author(s)

Richard M. P. Veenboer, Alba Collado, Stephanie Dupuy, Tomas Lebl, Laura Falivene, Luigi Cavallo, David B. Cordes, Alexandra M. Z. Slawin, Catherine S. J. Cazin, Steven P. Nolan

School/Research organisations

Abstract

The role of counterions in chemistry mediated by gold complexes stretches much further than merely providing charge balance to cationic gold species. Interplay between their basicities and coordination strengths influences interactions with both the gold center and substrates in catalysis. Actual monogold-(I) active species are generally believed to be monocoordinated species, formed from the abstraction or the decoordination of a second ligand from precursor complexes, but only a small amount of experimental evidence exists to underpin the existence of these transient species. The formation of a bench-stable neutral IPrCI-gold(I) tetrafluoroborate complex is reported herein. Experimental studies by X-ray diffraction analysis and NMR spectroscopy and theoretical studies by DFT calculations were conducted to determine the composition, structure, and behavior of this complex. The absence of an auxiliary ligand resulted in inner-sphere coordination of the counterion in the solid state. In solution, an equilibrium between two conformations was found with the counterion occupying inner-sphere and outer-sphere positions, respectively. Stoichiometric and catalytic reactivity studies with the tetrafluoroborate complex have been conducted. These confirmed the lability of the inner-sphere coordinating counterion that gives the IPrCI-gold(I) fragment behavior similar to that of related systems.

Close

Details

Original languageEnglish
Pages (from-to)2861-2869
Number of pages9
JournalOrganometallics
Volume36
Issue number15
Early online date20 Jul 2017
DOIs
StatePublished - 14 Aug 2017

    Research areas

  • N-heterocyclic carbene, Silver-free protocols, Gold catalysis, Gold(III) complexes, Reaction-mechanism, Highly efficient, Stereoselective hydrocarboxylation, Alkynes, Counterion, NHC

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

View graph of relations

Related by author

  1. Synthesis, characterization and optoelectronic properties of iridium complexes bearing nonconjugated six-membered chelating ligands

    Hierlinger, C., Pal, A. K., Stella, F., Lebl, T., Cordes, D. B., Slawin, A. M. Z., Jacquemin, D., Guerchais, V. & Zysman-Colman, E. 19 Feb 2018 In : Inorganic Chemistry. 57, 4, p. 2023-2034

    Research output: Research - peer-reviewArticle

  2. Synthesis of the natural product descurainolide and cyclic peptides from lignin-derived aromatics

    Ojo, O. S., Nardone, B., Musolino, S. F., Neal, A., Wilson, L., Lebl, T., Slawin, A. M. Z., Cordes, D. B., Taylor, J. E., Naismith, J. H., Smith, A. D. & Westwood, N. J. 14 Jan 2018 In : Organic & Biomolecular Chemistry. 16, 2, p. 266-273

    Research output: Research - peer-reviewArticle

  3. Use of bisulfite processing to generate high-β-O-4 content water-soluble lignosulfonates

    Miles-Barrett, D. M., Montgomery, J. R. D., Lancefield, C. S., Cordes, D. B., Slawin, A. M. Z., Lebl, T., Carr, R. & Westwood, N. J. 6 Feb 2017 In : ACS Sustainable Chemistry & Engineering . 5, 2, p. 1831-1839 9 p.

    Research output: Research - peer-reviewArticle

  4. The synthesis and analysis of lignin-bound Hibbert ketone structures in technical lignins

    Miles-Barrett, D., Neal, A., Hand, C., Montgomery, J., Panovic, I., Ojo, O. S., Lancefield, C. S., Cordes, D. B., Slawin, A. M. Z., Lebl, T. & Westwood, N. J. 14 Nov 2016 In : Organic & Biomolecular Chemistry. 14, 42, p. 10023-10030 8 p.

    Research output: Research - peer-reviewArticle

Related by journal

  1. Synthesis, Characterization, and Catalytic Properties of Iridium Pincer Complexes Containing NH Linkers

    Leveson-Gower, R. B., Webb, P. B., Cordes, D. B., Slawin, A. M. Z., Smith, D. M., Tooze, R. P. & Liu, J. 8 Jan 2018 In : Organometallics. 37, 1, p. 30-39 10 p.

    Research output: Research - peer-reviewArticle

  2. Expedient syntheses of neutral and cationic Au(I)–NHC complexes

    Veenboer, R. M. P., Gasperini, D., Nahra, F., Cordes, D. B., Slawin, A. M. Z., Cazin, C. S. J. & Nolan, S. P. 25 Sep 2017 In : Organometallics. 36, 18, p. 3645–3653

    Research output: Research - peer-reviewArticle

  3. Selective oxidation and functionalization of 6‑diphenylphosphinoacenaphthyl-5-tellurenyl species 6‑Ph2P‑Ace-5-TeX (X = Mes, Cl, O3SCF3). Various types of P−E···Te(II,IV) bonding situations (E = O, S, Se)

    Hupf, E., Do, T. G., Nordheider, A., Wehrhahn, M., Sanz Camacho, P., Ashbrook, S. E. M., Lork, E., Slawin, A. M. Z., Mebs, S., Woollins, J. D. & Beckmann, J. 24 Apr 2017 In : Organometallics. 36, 8, p. 1566–1579

    Research output: Research - peer-reviewArticle

  4. Isolation of [Ru(IPr)2(CO)H]+ (IPr = 1,3-Bis(2,6-diisopropylphenyl)imidazol-2-ylidene) and Reactivity toward E–H (E = H, B) Bonds

    Riddlestone, I. M., McKay, D., Gutmann, M. J., Macgregor, S. A., Mahon, M. F., Sparkes, H. A. & Whittlesey, M. K. 9 May 2016 In : Organometallics. 35, 9, p. 1301-1312 12 p.

    Research output: Research - peer-reviewArticle

ID: 251051913