Conformationally-locked metallomacrocycles-prototypes for a novel type of axial chirality

Chow, Hoi Shan and Constable, Edwin C. and Frantz, Richard and Housecroft, Catherine E. and Lacour, Jérôme and Neuburger, Markus and Rappoport, Dmitrij and Schaffner, Silvia. (2009) Conformationally-locked metallomacrocycles-prototypes for a novel type of axial chirality. New Journal of Chemistry, 33 (2). pp. 376-385.

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Official URL: http://edoc.unibas.ch/dok/A5251511

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A series of ditopic ligands incorporating two 2,2':6',2 ''-terpyridine (tpy) metal-binding domains linked to a central naphthalenediyl core by ethyleneoxy chains of various lengths have been prepared and their iron(II) complexes prepared. The major thermodynamic products of complexation are ferracycles of [1 + 1], [2 + 2] or [3 + 3] stoichiometry. In the case of the [1 + 1] complexes, the linker between the two tpy domains is spatially restricted and the cations exhibit chirality associated with the conformation about the central N-Fe-N bonds. The dynamic processes by which the enantiomeric forms interconvert are investigated in the presence of chiral anions by NMR and circular dichroism spectroscopy making use of the Pfeiffer effect. We have shown that ditopic bis(2,2':6',2 ''-terpyridine) ligands give rise to conformationally restricted complexes with iron(II) centres. The absolute configuration of the cations in the diastereomeric ion pairs obtained through the Pfeiffer effect has been calculated using TDDFT methods.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Constable)
UniBasel Contributors:Constable, Edwin Charles and Housecroft, Catherine Elizabeth and Neuburger, Markus
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Royal Society of Chemistry
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:08 May 2017 09:02
Deposited On:22 Mar 2012 14:07

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