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Inorg Chem. 2015 Jul 20;54(14):6986-92. doi: 10.1021/acs.inorgchem.5b00940. Epub 2015 Jun 30.

Post-Assembly Covalent Di- and Tetracapping of a Dinuclear [Fe2L3](4+) Triple Helicate and Two [Fe4L6](8+) Tetrahedra Using Sequential Reductive Aminations.

Inorganic chemistry

Christopher R K Glasson, George V Meehan, Murray Davies, Cherie A Motti, Jack K Clegg, Leonard F Lindoy

Affiliations

  1. §The Australian Institute of Marine Science, Townsville, Queensland 4810, Australia.
  2. ‡School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane St. Lucia, Queensland 4072 Australia.
  3. #School of Chemistry, The University of Sydney, Building F11 Eastern Avenue, Sydney, New South Wales 2006, Australia.

PMID: 26125324 DOI: 10.1021/acs.inorgchem.5b00940

Abstract

The use of a highly efficient reductive amination procedure for the postsynthetic end-capping of metal-templated helicate and tetrahedral supramolecular structures bearing terminal aldehyde groups is reported. Metal template formation of a [Fe2L3](4+) dinuclear helicate and two [Fe4L6](8+) tetrahedra (where L is a linear ligand incorporating two bipyridine domains separated by one or two 1,4-(2,5-dimethoxyaryl) linkers and terminated by salicylaldehyde functions is described. Postassembly reaction of each of these "open" di- and tetranuclear species with excess ammonium acetate (as a source of ammonia) and sodium cyanoborohydride results in a remarkable reaction sequence whereby the three aldehyde groups terminating each end of the helicate, or each of the four vertices of the respective tetrahedra, react with ammonia then undergo successive reductive amination to yield corresponding fully tertiary-amine capped cryptate and tetrahedral covalent cages.

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