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2021-02-02Zeitschriftenartikel DOI: 10.1002/chem.202004945
Structural Determination of an Unusual CuI‐Porphyrin‐π‐Bond in a Hetero‐Pacman Cu‐Zn‐Complex
Marquardt, Michael cc
Cula, Beatrice cc
Budhija, Vishal cc
Dallmann, André
Schwalbe, Matthias cc
Mathematisch-Naturwissenschaftliche Fakultät
The synthesis and characterization of a hetero-dinuclear compound is presented, in which a copper(I)trishistidine type coordination unit is positioned directlyabove a zinc porphyrin unit. The close distance betweenthe two coordination fragments is secured by a rigid xan-thene backbone, and a unique (intramolecular) copperporphyrin-p-bond was determined for the first time in themolecular structure. This structural motif was further ana-lyzed by temperature-dependent NMR studies: In solutionat room temperature the coordinative bond fluctuates,while it can be frozen at low temperatures. Preliminary re-activity studies revealed a reduced reactivity of the cop-per(I) moiety towards dioxygen. The results adumbratewhy nature is avoiding metal porphyrin-p-bonds by fixingreactive metal centers in a predetermined distance toeach other within multimetallic enzymatic reaction cen-ters.
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(CC BY-NC-ND 4.0) Attribution-NonCommercial-NoDerivatives 4.0 International(CC BY-NC-ND 4.0) Attribution-NonCommercial-NoDerivatives 4.0 International(CC BY-NC-ND 4.0) Attribution-NonCommercial-NoDerivatives 4.0 International(CC BY-NC-ND 4.0) Attribution-NonCommercial-NoDerivatives 4.0 International
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DOI
10.1002/chem.202004945
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https://doi.org/10.1002/chem.202004945
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<a href="https://doi.org/10.1002/chem.202004945">https://doi.org/10.1002/chem.202004945</a>