Getting harder: cobalt (III)-template synthesis of catenanes and rotaxanes

Leigh, D. A., Lusby, P. J., McBurney, R. T., Morelli, A., Slawin, A. M.Z., Thomson, A. R. and Walker, D. B. (2009) Getting harder: cobalt (III)-template synthesis of catenanes and rotaxanes. Journal of the American Chemical Society, 131(10), pp. 3762-3771. (doi:10.1021/ja809627j) (PMID:19275264)

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Abstract

The synthesis of catenanes and rotaxanes using the hard trivalent transition metal ion cobalt(III) as a template is reported. Tridentate dianionic pyridine-2,6-dicarboxamido ligands, each with two terminal alkene groups, coordinate Co(III) in a mutually orthogonal arrangement such that entwined or interlocked molecular architectures are produced by ring-closing olefin metathesis. Double macrocyclization of two such ligands bound to Co(III) afford a non-interlocked “figure-of-eight” complex in 42% yield, the structure determined by X-ray crystallography. Preforming one macrocycle and carrying out a single macrocyclization of the second bis-olefin with both ligands attached to the Co(III) template led to the isomeric [2]catenate in 69% yield. The mechanically interlocked structure was confirmed by X-ray crystallography of both the Co(III) catenate and the metal-free catenand. A Co(III)-template [2]rotaxane was assembled in 61% yield by macrocyclization of the bis-olefin ligand about an appropriate dianionic thread. For both catenanes and rotaxanes, removal of the metal ion via reduction under acidic conditions to the more labile Co(II) gave neutral interlocked molecules with well-defined co-conformations stabilized by intercomponent hydrogen bonding.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Thomson, Dr Drew and Mcburney, Dr Roy
Authors: Leigh, D. A., Lusby, P. J., McBurney, R. T., Morelli, A., Slawin, A. M.Z., Thomson, A. R., and Walker, D. B.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of the American Chemical Society
Publisher:American Chemical Society
ISSN:0002-7863
ISSN (Online):1520-5126
Published Online:24 February 2009

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