Skip to content

Research at St Andrews

Chiral wide bite angle diphosphine ligands: synthesis, coordination chemistry and application in Pd-catalyzed allylic alkylation

Research output: Contribution to journalArticle


Open Access permissions



Christine Czauderna, Amanda Jarvis, Frank Heutz, David Bradford Cordes, Alexandra Martha Zoya Slawin, Jarl Ivar van der Vlugt, Paul C J Kamer

School/Research organisations


A series of diphosphine ligands bearing ester- and ether-modified diphenylether backbones have been prepared. The introduction of carboxylic acid or ether auxiliaries in the ortho-positions relative to the diphenylphosphine groups was achieved via straightforward four-step synthetic protocols, prior to introduction of the phosphines. The electronic properties of these backbone-modified DPEPhos ligands were evaluated by probing the relevant carbonyl stretching frequencies (νCO) of Ni(CO)2(PP) species (PP = diphosphine) using IR spectroscopy and by determining the phosphorus-selenium coupling constant JSe-P of phosphine selenide derivatives using 31P{1H} NMR spectroscopy. Also the X-ray structure for the bis(carbonyl)nickel(0) species with one of the ligands is reported. The [Pd(η3-allyl)(PP)]-complexes were characterized by multinuclear NMR spectroscopy and applied in the asymmetric allylic alkylation of l,3-diphenyl-2-propenyl acetate and cyclohex-2-enyl acetate with dimethyl malonate in order to benchmark their catalytic potential. The enantioselectivity (ranging from 3 to 70 %) was found to depend on the size of the chiral auxiliary introduced within the diphenyl ether backbone and its proximity to the phosphorus donor groups and hence to the active metal centre. These studies revealed that substituents on the backbone have only a minor effect on the electronic character of the diphenylphosphine groups.



Original languageEnglish
Pages (from-to)1608-1618
Issue number9
Early online date30 Apr 2015
Publication statusPublished - 11 May 2015

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

View graph of relations

Related by author

  1. Preventing undesirable structure flexibility in pyromellitate metal organic frameworks

    Duncan, M. J., Hayes, O. G., Slawin, A. M. Z., Cordes, D. B., Morris, R. E. & Warrender, S. J., 27 May 2020, In : European Journal of Inorganic Chemistry. Early View, 9 p.

    Research output: Contribution to journalArticle

Related by journal

  1. Redox noninnocent nature of acridine-based Pincer complexes of 3d metals and C–C bond formation

    Daw, P., Kumar, A., Oren, D., Espinosa-Jalapa, N. A., Srimani, D., Diskin-Posner, Y., Leitus, G., Shimon, L., Carmieli, R., Ben-David, Y. & Milstein, D., 27 Jan 2020, In : Organometallics. 39, 2, p. 279-285

    Research output: Contribution to journalArticle

  2. Structure and dynamics of iron pentacarbonyl

    Portius, P., Buehl, M., George, M., Grevels, F-W. & Turner, J., 11 Nov 2019, In : Organometallics. 38, 21, p. 4288-4297 10 p.

    Research output: Contribution to journalArticle

  3. 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: Contribution to journalArticle

  4. 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: Contribution to journalArticle

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

    Veenboer, R. M. P., Collado, A., Dupuy, S., Lebl, T., Falivene, L., Cavallo, L., Cordes, D. B., Slawin, A. M. Z., Cazin, C. S. J. & Nolan, S. P., 14 Aug 2017, In : Organometallics. 36, 15, p. 2861-2869 9 p.

    Research output: Contribution to journalArticle

ID: 181751317