chem_201101551_sm_movie1.mpeg (2.09 MB)
Cu(II) is reduced to Cu(I) without external reductants
Version 2 2016-07-09, 16:28
Version 1 2016-07-09, 16:16
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posted on 2016-07-09, 16:28 authored by gloria tabacchigloria tabacchi, Davide Barreca, Ettore Fois, Alberto Gasparotto, Roberta Seraglia, Eugenio TondelloMovie showing the Cu(II)-to-Cu(I) intramolecular reduction in a copper(II) complex.
The reaction involves a copper(II) complex, which bears a diamine ligand and a diketonate ligand. The complex is planar and positively charged (+1).
Atom colors: Cu=yellow, F=green, O=red, N=blue, C=grey, H=white. The atoms of the diamine C*-H* bond (which breaks homolytically during the reaction) are highlighted as bigger spheres. The oxygen atom O* (which accepts the hydrogen atom H*) is highlighted as a bigger magenta sphere.
Description of the movie:
- In the first phases of the reduction reaction, the copper complex switches from a square-planar to a twisted-tetrahedral geometry.
- An out-of-plane rotation (180 degrees) of the diketonate ligand occurs.
- The C*H* bond of the diamine gradually approaches the oxygen atom O* of the diketonate, while becoming increasingly elongated and closer to the metal center.
- The C*H* bond, now fully activated, displaces the diketonate oxygen away from its coordination position.
Now, the H* is on the fly between the two ligands, and the diamine acts as a polydentate ligand towards the copper center.
- The binding of H* to the diketonate oxygen O* leads to a beta-diketone enol and to an alpha-dehydrogenated diamine.
- A six-membered ring is formed through the C terminal of the amine, which is coordinated to the copper center.
- The neutral diketone ligand finally leaves the Cu-ring structure.
At the beginning of the reaction, Cu is in the Cu(II) oxidation state.
In the transition state, the spin density distribution showed: 1) the formation of a radical moiety, which proved that the C*-H* bond cleavage is homolytic; 2) that the O-H bond formation is accompanied by a simultaneous electron transfer to Cu, which is reduced to Cu(I)
At the end of the reaction, the oxidation state of copper is Cu(I), as proved by calculations.
This reaction is described in the article:
How Does Cu-II Convert into Cu-I: An Unexpected Ring-Mediated Single-Electron Reduction.
Published in:
Chem. Eur. J., 17: 10864–10870.
doi:10.1002/chem.201101551
A green open access version of the paper is available at this link: https://figshare.com/articles/How_Does_Cu_II_Convert_into_Cu_I_/3478880
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copper catalystCucopperMass Spectrometric Studyesi-msESI-MSdensity functional theorydensity functional calculationstheoretical chemistry computationsmodeling and simulationcopper reactivityfragmentation productsfragmentation pathwaysCH activation reactionsReaction mechanismsreduction processintramolecular redox reactionredox chemistryredox processestransition metal compoundsTransition metal complexescopper catalyzed reactionsintramolecular electron transfer reactionscomputational chemistrytransition state structuresring shapecyclic compoundschemical vapor depositionPrecursor Fragment Concentrationsintramolecular reductive cyclizationcyclizationcomputational modelsFirst principles molecular dynamicsAnalytical Chemistry not elsewhere classifiedAnalytical SpectrometryChemical Thermodynamics and EnergeticsChemical Sciences not elsewhere classifiedChemical Characterisation of MaterialsComputational ChemistryFree Radical ChemistryInorganic ChemistryInorganic Chemistry not elsewhere classifiedNanochemistry and Supramolecular ChemistryOrganic ChemistryOrganic Chemistry not elsewhere classifiedPhysical Chemistry not elsewhere classifiedPhysical Chemistry of MaterialsPhysical Organic ChemistryReaction Kinetics and DynamicsTheoretical and Computational Chemistry not elsewhere classifiedTheory and Design of MaterialsTransition Metal ChemistryNanotechnology not elsewhere classifiedNanofabrication, Growth and Self AssemblyNanomaterials
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