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

Bell, CA, Bernhardt, PV, Gahan, LR, Martinez, M, Monteiro, MJ, Rodriguez, C and Sharrad, CA (2010) Copper(II) complexes of a hexadentate mixed-donor N3S3 macrobicyclic cage: Facile rearrangements and interconversions. Chemistry: A European Journal, 16 10: 3166-3175. doi:10.1002/chem.200902611


Author Bell, CA
Bernhardt, PV
Gahan, LR
Martinez, M
Monteiro, MJ
Rodriguez, C
Sharrad, CA
Title Copper(II) complexes of a hexadentate mixed-donor N3S3 macrobicyclic cage: Facile rearrangements and interconversions
Formatted title
Copper(II) complexes of a hexadentate mixed-donor N3S3 macrobicyclic cage: Facile rearrangements and interconversions
Journal name Chemistry: A European Journal   Check publisher's open access policy
ISSN 0947-6539
1521-3765
Publication date 2010-03-08
Sub-type Article (original research)
DOI 10.1002/chem.200902611
Volume 16
Issue 10
Start page 3166
End page 3175
Total pages 10
Place of publication Weinheim, Germany
Publisher Wiley
Collection year 2011
Language eng
Formatted abstract
The potentially hexadentate mixed-donor cage ligand l-methyl-8-amino-3, 13, 16-trithia-6, 10, 19-triazabi-cyclo[6.6.6]eicosane (AMME-N3S3sar; sar = sarcophagine) displays variable coordination modes in a complex with copper(II). In the absence of coordi-nating anions, the ligand adopts a con-ventional hexadentate N3S3 binding mode in the complex [Cu(AMME-N3S3sar](ClO4)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-N3S3sar)Br]+ is observed that features a novel tetradentate (N2S2)-coordinated form of the cage ligand. This copper(II) complex has also been characterized by X-ray crys-tallography and solution spectroscopy. The mechanism of the reversible inter-conversion 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. Electrochemis-try of both [Cu(AMME-N3S 3sar)]2+ and [Cu(AMME-N3S3sar)Br] + in DMSO shows that upon reduction to the monovalent state, they share a common five-coordinated form in which the ligand is bound to copper in a tetradentate form exclusively, regard-less of whether a six- or five-coordinat-ed copper(II) complex is the precursor. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.
Keyword Bromine
Age compounds
Copper
EPR spectroscopy
Macrocycles
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2011 Collection
School of Chemistry and Molecular Biosciences
 
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Created: Sun, 11 Apr 2010, 10:06:58 EST