Skip to content

Research at St Andrews

Geminally substituted tris(acenaphthyl) and bis(acenaphthyl) arsines, stibines and bismuthine: a structural and Nuclear Magnetic Resonance investigation

Research output: Contribution to journalArticle


Open Access permissions



Brian Alexander Chalmers, Christina Meigh, Phillip Nejman, Michael Buehl, Tomas Lebl, J Derek Woollins, Alexandra Martha Zoya Slawin, Petr Kilian

School/Research organisations


Tris(acenaphthyl) and bis(acenaphthyl) substituted pnictogens (iPr2P-Ace)3E (24) (E = As, Sb, Bi; Ace = acenaphthene-5,6-diyl) and (iPr2P-Ace)2EPh (5 and 6), (E = As, Sb) were synthesised and fully characterised by multinuclear NMR, HRMS, elemental analysis and single crystal X-ray diffraction. The molecules adopt propeller-like geometries with the restricted rotational freedom of the sterically encumbered iPr2P-Ace groups resulting in distinct NMR features. In the tris(acenaphthyl) species (24) the phosphorus atoms are isochronous in the 31P{1H} NMR spectra, and the rotation of the three acenaphthyl moieties around E–Cipso bond is locked. On the other hand, the bis(acenaphthyl) species show a fluxional behaviour, resulting in an AX to A2 spin system transition in the 31P{1H} VT NMR spectra. This allowed elucidation of remarkable through-space couplings of 8TSJPP 11.5 Hz (for 5) and 25.8 Hz (for 6) at low temperature. In addition, detailed lineshape analysis of the thermodynamic parameters of the restricted rotation of the “propeller blades” in 5 was performed in the intermediate temperature region and also at coalescence. The lone pairs on the pnictogen atoms in 26 are oriented such that they form a bowl shaped area which is somehow buried within the molecule.


Original languageEnglish
Pages (from-to)7117-7125
Number of pages9
JournalInorganic Chemistry
Issue number14
Early online date24 Jun 2016
StatePublished - 18 Jul 2016

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

View graph of relations

Related by author

  1. Hydride abstraction and deprotonation – an efficient route to low co-ordinate phosphorus and arsenic species

    Taylor, L. J., Buehl, M., Wawrzyniak, P., Chalmers, B. A., Woollins, J. D., Slawin, A. M. Z., Fuller, A. & Kilian, P. 2015 In : European Journal of Inorganic Chemistry. Early view

    Research output: Contribution to journalArticle

  2. Reactivity profile of a peri-substitution-stabilized phosphanylidene-phosphorane: synthetic, structural, and computational studies

    Surgenor, B. A., Chalmers, B. A., Athukorala Arachchige, K. S., Slawin, A. M. Z., Woollins, J. D., Buehl, M. & Kilian, P. 9 Jun 2014 In : Inorganic Chemistry. 53, 13, p. 6856–6866 11 p.

    Research output: Contribution to journalArticle

  3. Sterically restricted tin phosphines, stabilized by weak intramolecular donor-acceptor interactions

    Arachchige, K. S. A., Camacho, P. S., Ray, M. J., Chalmers, B. A., Knight, F. R., Ashbrook, S. E., Buehl, M., Kilian, P., Slawin, A. M. Z. & Woollins, J. D. 26 May 2014 In : Organometallics. 33, 10, p. 2424-2433 10 p.

    Research output: Contribution to journalArticle

Related by journal

  1. Visible and near-infrared emission from lanthanoid β-triketonate assemblies incorporating cesium cations

    Galán, L. A., Reid, B. L., Stagni, S., Sobolev, A. N., Skelton, B. W., Cocchi, M., Malicka, J. M., Zysman-Colman, E., Moore, E. G., Ogden, M. I. & Massi, M. 7 Aug 2017 In : Inorganic Chemistry. 56, 15, p. 8975-8985 11 p.

    Research output: Contribution to journalArticle

  2. An unprecedented family of luminescent iridium(III) complexes bearing a six-membered chelated tridentate C^N^C ligand

    Hierlinger, C., Roisnel, T., Cordes, D. B., Slawin, A. M. Z., Jacquemin, D., Guerchais, V. & Zysman-Colman, E. 1 May 2017 In : Inorganic Chemistry. 56, 9, p. 5182–5188

    Research output: Contribution to journalArticle

  3. Investigating unusual homonuclear intermolecular “through-space” J couplings in organochalcogen systems

    Sanz Camacho, P., McKay, D., Dawson, D. M., Kirst, C., Yates, J. R., Green, T. F. G., Cordes, D. B., Slawin, A. M. Z., Woollins, J. D. & Ashbrook, S. E. 7 Nov 2016 In : Inorganic Chemistry. 55, 21, p. 10881-10887 7 p.

    Research output: Contribution to journalArticle

ID: 243729568