Fine‐Tuning the Electronic Properties of Highly Stable Organometallic CuIII Complexes Containing Monoanionic Macrocyclic Ligands
- 9 August 2005
- journal article
- research article
- Published by Wiley in Chemistry – A European Journal
- Vol. 11 (17), 5146-5156
- https://doi.org/10.1002/chem.200500088
Abstract
A family of highly stable organometallic CuIII complexes with monoanionic triazamacrocyclic ligands (Li) with general formula [CuLi]+ have been prepared and isolated, and their structural, spectroscopic, and redox properties thoroughly investigated. The HLi ligands have been designed in order to understand and quantify the electronic effects exerted by electron donor and electron‐withdrawing groups on either the aromatic ring or the central secondary amine or on both. In the solid state the CuIII complexes were mainly characterized by single‐crystal X‐ray diffraction analysis, whereas in solution their structural characterization was mainly based on 1H NMR spectroscopy given the diamagnetic nature of the d8 square‐planar CuIII complexes. Cyclic voltammetry together with 1H NMR and UV/Vis spectroscopy have allowed us to quantify the electronic effects exerted by the ligands on the CuIII metal center. A theoretical analysis of this family of CuIII complexes has also been undertaken by DFT calculations to gain a deeper insight into the electronic structure of these complexes, which has in turn allowed a greater understanding of the nature of the UV/Vis transitions as well as the molecular orbitals involved.Keywords
This publication has 55 references indexed in Scilit:
- Cu(II)Gly2HisGly Oxidation by H2O2/Ascorbic Acid to the Cu(III) Complex and Its Subsequent Decay to Alkene PeptidesInorganic Chemistry, 2003
- Understanding and exploiting C–H bond activationNature, 2002
- Implementation of time-dependent density functional response equationsComputer Physics Communications, 1999
- Activation of C−H Bonds by Metal ComplexesChemical Reviews, 1997
- On the Structure, Electrochemistry, and Spectroscopy of the (N,N‘-Bis(2‘-(dimethylamino)ethyl)-N,N‘-dimethylpropane-1,3- diamine)copper(II) IonJournal of the American Chemical Society, 1997
- The First Stable Copper(III) Complex Containing Aliphatic Thiolates as Ligands: Structural and Spectroscopic Evidence for CuII and CuIII Ions in Complexes with Square‐Planar CuN2S2 Coordination EnvironmentsAngewandte Chemie-International Edition, 1996
- Der erste stabile Kupfer(III)‐Komplex mit aliphatischen Thiolaten als Liganden: struktureller und spektroskopischer Nachweis von CuII‐ und CuIII‐Ionen in Komplexen mit quadratisch‐planaren CuN2S2‐KoordinationssphärenAngewandte Chemie, 1996
- An efficient synthesis of polyaza[n]paracyclophanesThe Journal of Organic Chemistry, 1993
- Comparison of the influence of saturated nitrogen and sulfur donor atoms on the properties of copper(II/I)-macrocyclic polyamino polythiaether ligand complexes: redox potentials and protonation and stability constants of CuIL species and new structural dataInorganic Chemistry, 1992
- Roothaan-Hartree-Fock-Slater atomic wave functionsAtomic Data and Nuclear Data Tables, 1981