Skip to content

Research at St Andrews

Sterically encumbered tin and phosphorus peri-substituted acenaphthenes

Research output: Contribution to journalArticle


Open Access permissions



Brian Alexander Chalmers, Kasun Sankalpa Athukorala Arachchige, Joanna Prentis, Fergus Ross Knight, Petr Kilian, Alexandra Martha Zoya Slawin, J Derek Woollins

School/Research organisations


A group of sterically encumbered peri-substituted acenaphthenes have been prepared, containing tin moieties at the 5,6-positions in 13 ([Acenap(SnR3)2], Acenap = acenaphthene-5,6-diyl; R3 = Ph3 (1), Me3 (2); [(Acenap)2(SnMe2)2] (3)) and phosphorus functional groups at the proximal peri-positions in 4 and 5 ([Acenap(PR2)(PiPr2)] R2 = Ph2 (4), Ph(iPr) (5)). Bis(stannane) structures 13 are dominated by repulsive interactions between the bulky tin groups, leading to peri-distances approaching the sum of van der Waals radii. Conversely, the quasi-linear CPh-P···P three-body fragments found in bis(phosphine) 4 suggest the presence of a lp(P)−σ*(P–C) donor–acceptor 3c-4e type interaction, supported by a notably short intramolecular P···P distance and notably large JPP through-space coupling (180 Hz). Severely strained bis(sulfides) 4-S and 5-S, experiencing pronounced in-plane and out-of-plane displacements of the exocyclic peri-bonds, have also been isolated following treatment of 4 and 5 with sulfur. The resulting nonbonded intramolecular P···P distances, ∼4.05 Å and ∼12% longer than twice the van der Waals radii of P (3.60 Å), are among the largest ever reported peri-separations, independent of the heteroatoms involved, and comparable to the distance found in 1 containing the larger Sn atoms (4.07 Å). In addition we report two metal complexes with square planar [(4)PtCl2] (4-Pt) and octahedral cis-[(4)Mo(CO)4] (4-Mo) geometries. In both complexes the bis(phosphine) backbone is distorted, but notably less so than in bis(sulfide) 4-S. All compounds were fully characterized, and except for bis(phosphine) 5, crystal structures were determined.


Original languageEnglish
Pages (from-to)8795-8808
Number of pages14
JournalInorganic Chemistry
Issue number16
Publication statusPublished - 31 Jul 2014

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

View graph of relations

Related by author

  1. A study of through-space and through-bond JPP coupling in a rigid nonsymmetrical bis(phosphine) and its metal complexes

    Chalmers, B. A., Nejman, P. L., Llewellyn, A. V., Felaar, A. M., Griffiths, B. L., Portman, E. I., Gordon, E-J. L., Fan, K. J. H., Woollins, J. D., Buehl, M., Malkina, O. L., Cordes, D. B., Slawin, A. M. Z. & Kilian, P., 19 Mar 2018, In : Inorganic Chemistry. 57, 6, p. 3387-3398 12 p.

    Research output: Contribution to journalArticle

  2. Dealkanative main group couplings across the peri-gap

    Taylor, L. J., Buehl, M., Chalmers, B. A., Ray, M. J., Wawrzyniak, P., Walton, J. C., Cordes, D. B., Slawin, A. M. Z., Woollins, J. D. & Kilian, P., 27 Dec 2017, In : Journal of the American Chemical Society. 139, 51, p. 18545-18551

    Research output: Contribution to journalArticle

  3. Optimised synthesis and characterisation of 1-adamantyltrimethylphosphonium iodide

    Mansour, R., Nejman, P., Taylor, L. J., Chalmers, B. A., Rey, F., Bengueddach, A., Woollins, J. D., Slawin, A. M. Z. & Kilian, P., 5 Sep 2017, In : Polyhedron. 133, p. 302-306 5 p.

    Research output: Contribution to journalArticle

Related by journal

  1. Ab initio molecular dynamics investigation of beryllium complexes

    Raymond, O., Buehl, M., Lane, J., Henderson, W., Brothers, P. & Plieger, P., 4 Feb 2020, In : Inorganic Chemistry. Articles ASAP

    Research output: Contribution to journalArticle

  2. Synthesis and polymorphism of mixed aluminium-gallium oxides

    Cook, D. S., Hooper, J. E., Dawson, D. M., Fisher, J. M., Thompsett, D., Ashbrook, S. E. M. & Walton, R. I., 24 Feb 2020, In : Inorganic Chemistry. Article ASAP

    Research output: Contribution to journalArticle

  3. A gadolinium spin label with both a narrow central transition and short tether for use in double electron electron resonance distance measurements

    Shah, A., Roux, A., Starck, M., Mosely, J. A., Stevens, M., Norman, D. G., Hunter, R. I., El Mkami, H., Smith, G., Parker, D. & Lovett, J. E., 18 Feb 2019, In : Inorganic Chemistry. Article ASAP

    Research output: Contribution to journalArticle

  4. Crystallographic insights into the behavior of highly acidic metal cations in ionic liquids from ractions of titanium tetrachloride with [1-butyl-3-methylimidazolium][X] ionic liquids (X = chloride, bromide, tetrafluoroborate)

    Mishra, M. K., Kelley, S. P., Dilip, M., Vaid, T. P., Cordes, D. B., Griffin, S. T. & Rogers, R. D., 4 Feb 2019, In : Inorganic Chemistry. 58, 3, p. 1764-1773

    Research output: Contribution to journalArticle

ID: 192592823