Copper(II) complexes of a hexadentate mixed-donor N3S3 macrobicyclic cage: facile rearrangements and interconversions

Chemistry : a European Journal
Craig A BellClint A Sharrad

Abstract

The potentially hexadentate mixed-donor cage ligand 1-methyl-8-amino-3,13,16-trithia-6,10,19-triazabicyclo[6.6.6]eicosane (AMME-N(3)S(3)sar; sar=sarcophagine) displays variable coordination modes in a complex with copper(II). In the absence of coordinating anions, the ligand adopts a conventional hexadentate N(3)S(3) binding mode in the complex [Cu(AMME-N(3)S(3)sar)](ClO(4))(2) that is typical of cage ligands. This structure was determined by X-ray crystallography and solution spectroscopy (EPR and NIR UV/Vis). However, in the presence of bromide ions in DMSO, clean conversion to a five-coordinate bromido complex [Cu(AMME-N(3)S(3)sar)Br](+) is observed that features a novel tetradentate (N(2)S(2))-coordinated form of the cage ligand. This copper(II) complex has also been characterized by X-ray crystallography and solution spectroscopy. The mechanism of the reversible interconversion between the six- and five-coordinated copper(II) complexes has been studied and the reaction has been resolved into two steps; the rate of the first is linearly dependent on bromide ion concentration and the second is bromide independent. Electrochemistry of both [Cu(AMME-N(3)S(3)sar)](2+) and [Cu(AMME-N(3)S(3)sar)Br](+) in DMSO shows that upon redu...Continue Reading

References

Dec 26, 2001·Chemical Reviews·K Matyjaszewski, J Xia
May 2, 2002·Journal of the American Chemical Society·Virgil PercecCatherine M Mitchell
Mar 14, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Paul V BernhardtAlan M Sargeson
May 24, 2008·Chemical Society Reviews·Tomislav Pintauer, Krzysztof Matyjaszewski

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Citations

Dec 10, 2013·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Maram T BashaPaul V Bernhardt
Jul 9, 2013·Journal of Inorganic Biochemistry·Anders ThapperJosé J G Moura
Dec 20, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Paul V BernhardtMarta Vazquez
Nov 3, 2012·Inorganic Chemistry·Paul V BernhardtCarlos Rodríguez

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