2007
DOI: 10.1039/b612252c
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Comparative study of donor atom effects on the thermodynamic and electron-transfer kinetic properties of copper(ii/i) complexes with sexadentate macrocyclic ligands. [CuII/I([18]aneS4N2)] and [CuII/I([18]aneS4O2)]

Abstract: Studies have been conducted on the copper complexes formed with two sexadentate macrocyclic ligands containing four thioether sulfur donor atoms plus either two nitrogen or two oxygen donor atoms on opposing sides of the ring. The resulting two ligands, L, designated as [18]aneS(4)N(2) and [18]aneS(4)O(2), respectively, represent homologues of the previously studied Cu(ii/i) system with a macrocycle having six sulfur donor atoms, [18]aneS(6). Crystal structures of [Cu(II)([18]aneS(4)O(2))](ClO(4))(2) and [Cu(I… Show more

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Cited by 8 publications
(4 citation statements)
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“…The self-exchange rate constant, k 11 , for [Fe­(C 5 H 4 CH 3 ) 2 ] +/0 has been reported previously, using NMR analysis, to be (8.3 ± 0.8) × 10 6 M –1 s –1 . Using this value for k 11 , the self-exchange rate constant for [Co­(bpy) 3 ] 3+/2+ , k 22 , was calculated to be 0.27 ± 0.06 M –1 s –1 , which is in reasonable agreement with a literature value of 0.645 M –1 s –1 , especially considering that it was measured under similar, but different, conditions and crossed with a different redox couple. , The determined self-exchange rate constant for [Co­(bpy) 3 ] 3+/2+ was then used to determine a value of (9.1 ± 0.7) × 10 3 M –1 s –1 , k 33 , for the [Co­(ttcn) 2 ] 3+/2+ self-exchange reaction. A summary of the self-exchange rate constants can be found in Table .…”
Section: Resultsmentioning
confidence: 99%
“…The self-exchange rate constant, k 11 , for [Fe­(C 5 H 4 CH 3 ) 2 ] +/0 has been reported previously, using NMR analysis, to be (8.3 ± 0.8) × 10 6 M –1 s –1 . Using this value for k 11 , the self-exchange rate constant for [Co­(bpy) 3 ] 3+/2+ , k 22 , was calculated to be 0.27 ± 0.06 M –1 s –1 , which is in reasonable agreement with a literature value of 0.645 M –1 s –1 , especially considering that it was measured under similar, but different, conditions and crossed with a different redox couple. , The determined self-exchange rate constant for [Co­(bpy) 3 ] 3+/2+ was then used to determine a value of (9.1 ± 0.7) × 10 3 M –1 s –1 , k 33 , for the [Co­(ttcn) 2 ] 3+/2+ self-exchange reaction. A summary of the self-exchange rate constants can be found in Table .…”
Section: Resultsmentioning
confidence: 99%
“…The underlying idea is to design geometrically preorganized ligands with a suitable donor set that satisfies the electronic and steric requirements of Cu I , to yield mononuclear complexes exhibiting a tetrahedral geometry of the metal center. The reason for this resides in the possible exploitation of low-molecular-weight complexes as functional models of type-1 cupredoxins (electron-transfer copper proteins). Some of these models have recently been studied as electron-transfer mediators in dye-sensitized solar cells …”
Section: Introductionmentioning
confidence: 99%
“…However, in the presence of thiolated hyperbranched polyglycerols it becomes soluble, as confirmed by the direct visual observation of the resulting green solution and by the UV–vis spectrum shown in Figure . Several polythioether ligands that complex copper(II) have been reported to date, and a high complexation constant K Cu(II)‐thioether = 10 8 was found . In the absence of polymer, the UV–vis spectrum of the copper(II) precursor in methanol is characterized by a weak absorption band centered at 800 nm assigned to the well‐known d–d transition for Cu 2+ ions .…”
Section: Resultsmentioning
confidence: 99%