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Issue 10, 2015
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Pd-η3-C6H9 complexes of the Trost modular ligand: high nuclearity columnar aggregation controlled by concentration, solvent and counterion

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Abstract

Under optimised conditions, the Trost modular ligand (TML) series induces high levels of asymmetric induction in an extraordinarily wide range of reactions involving palladium π-allyl intermediates. Prior mechanistic investigations into reactions involving Pd-η3-C6H9 intermediates have focussed on the monomeric 13-membered ring formed via P,P-chelation of the ligand to Pd. However, it is also recognised that ring-opening oligomerisation provides a pool of high nuclearity Pd-η3-C6H9 species that, by affording a low level, or even the opposite sense, of asymmetric induction relative to the mononuclear species, are responsible for a reduction in selectivity under non-optimised conditions. Herein we describe an investigation by NMR spectroscopy, molecular mechanics, molecular dynamics, and small-angle neutron scattering (SANS), of a Pd-η3-C6H9 cation bearing the 1,2-diaminocyclohexane TML ligand (2). Using both nondeuterated and perdeuterated (D47) isotopologues of the resulting complexes ([1]+), we show that a two-stage oligomerisation-aggregation process forms self assembled cylindrical aggregates of very high nuclearity (up to 56 Pd centres). We also investigate how concentration, solvent and counter-anion all modulate the extent of oligomerisation.

Graphical abstract: Pd-η3-C6H9 complexes of the Trost modular ligand: high nuclearity columnar aggregation controlled by concentration, solvent and counterion

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Publication details

The article was received on 02 Apr 2015, accepted on 12 Jun 2015 and first published on 15 Jul 2015


Article type: Edge Article
DOI: 10.1039/C5SC01181G
Chem. Sci., 2015,6, 5793-5801
  • Open access: Creative Commons BY license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    Pd-η3-C6H9 complexes of the Trost modular ligand: high nuclearity columnar aggregation controlled by concentration, solvent and counterion

    D. T. Racys, J. Eastoe, P. Norrby, I. Grillo, S. E. Rogers and G. C. Lloyd-Jones, Chem. Sci., 2015, 6, 5793
    DOI: 10.1039/C5SC01181G

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