Formation of hybrid guanidine-stabilized bis(μ-oxo)dicopper cores in solution : Electronic and steric perturbations

A series of new hybrid peralkylated-amine-guanidine ligands based on a 1,3-propanediamine backbone and their Cu-O2 chemistry is reported. The copper(I) complexes react readily with O2 at low temperatures in aprotic solvents with weakly coordinating anions to form exclusively bis(μ-oxo) dicopper spec...

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Veröffentlicht in:European journal of inorganic chemistry. - 1998. - 2015(2015), 32 vom: 19. Nov., Seite 5426-5436
1. Verfasser: Herres-Pawlis, Sonja (VerfasserIn)
Weitere Verfasser: Haase, Roxana, Verma, Pratik, Hoffmann, Alexander, Kang, Peng, Stack, T Daniel P
Format: Aufsatz
Sprache:English
Veröffentlicht: 2015
Zugriff auf das übergeordnete Werk:European journal of inorganic chemistry
Schlagworte:Journal Article Copper Density Functional Theory Dioxygen Guanidine Ligands UV/Vis-Spectroscopy
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520 |a A series of new hybrid peralkylated-amine-guanidine ligands based on a 1,3-propanediamine backbone and their Cu-O2 chemistry is reported. The copper(I) complexes react readily with O2 at low temperatures in aprotic solvents with weakly coordinating anions to form exclusively bis(μ-oxo) dicopper species (O). Variation of the substituents on each side of the hybrid bidentate ligand highlights that less sterically demanding amine and guanidine substituents increase not only the thermal stability of the formed O cores but enhance inner-sphere phenolate hydroxylation pathways. TD-DFT analysis on selected guanidine-amine O species suggest that the additional visible feature observed is a guanidine π*→ Cu2O2 LMCT, which appears along with the classic oxo-ζu*→Cu(III) and πζ*→ Cu(III) LMCT transitions 
650 4 |a Journal Article 
650 4 |a Copper 
650 4 |a Density Functional Theory 
650 4 |a Dioxygen 
650 4 |a Guanidine Ligands 
650 4 |a UV/Vis-Spectroscopy 
700 1 |a Haase, Roxana  |e verfasserin  |4 aut 
700 1 |a Verma, Pratik  |e verfasserin  |4 aut 
700 1 |a Hoffmann, Alexander  |e verfasserin  |4 aut 
700 1 |a Kang, Peng  |e verfasserin  |4 aut 
700 1 |a Stack, T Daniel P  |e verfasserin  |4 aut 
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