Structural Characterization and Remarkable Axial Ligand Effect on the Nucleophilic Reactivity of a Nonheme Manganese(III)-Peroxo Complex

The dark side of the Mn: A manganese(III) complex bearing a 13-membered macrocyclic ligand (1, see picture) binds a peroxo ligand in a side-on η² fashion. The reactivity of 1 is influenced by the introduction of anionic ligands trans to the peroxo group. Electronic and structural changes upon trans-...

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Veröffentlicht in:Angewandte Chemie International Edition Jg. 48; H. 23; S. 4150 - 4153
Hauptverfasser: Annaraj, Jamespandi, Cho, Jaeheung, Lee, Yong-Min, Kim, Sung Yeon, Latifi, Reza, de Visser, Sam P, Nam, Wonwoo
Format: Journal Article
Sprache:Englisch
Veröffentlicht: Weinheim Wiley-VCH Verlag 25.05.2009
WILEY‐VCH Verlag
Schlagworte:
axial ligand effects
bioinorganic chemistry
Crystallography, X-Ray
enzyme models
Heme - chemistry
Ligands
manganese
Manganese - chemistry
Metalloporphyrins - chemistry
Molecular Structure
nucleophilic reactions
Peroxides - chemistry
ISSN:1433-7851, 1521-3773, 1521-3773
Online-Zugang:Volltext
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Zusammenfassung:The dark side of the Mn: A manganese(III) complex bearing a 13-membered macrocyclic ligand (1, see picture) binds a peroxo ligand in a side-on η² fashion. The reactivity of 1 is influenced by the introduction of anionic ligands trans to the peroxo group. Electronic and structural changes upon trans-ligand binding explain the increased nucleophilicity of the resulting complexes 1-X.
Bibliographie:http://dx.doi.org/10.1002/anie.200900118
These authors contributed equally to this work.
The research was supported by KOSEF/MEST through the CRI Program and the WCU project (R31‐2008‐000‐10010‐0) (to W.N.) and by CPU time provided by the National Service of Computational Chemistry Software (to S.P. de V.).
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content type line 23
ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.200900118