Formation of Hybrid Guanidine‐Stabilized Bis(μ‐oxo)dicopper Cores in Solution: Electronic and Steric Perturbations
- 22 October 2015
- journal article
- research article
- Published by Wiley in European Journal of Inorganic Chemistry
- Vol. 2015 (32) , 5426-5436
Abstract
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 reveal that less sterically demanding amine and guanidine substituents increase not only the thermal stability of the formed O cores but also enhance inner‐sphere phenolate hydroxylation pathways. TD‐DFT analysis on selected guanidine‐amine O species suggest that the additional visible‐wavelength feature observed is a guanidine π* → Cu2O2 LMCT, which appears along with the classic oxo‐σu* → CuIII and πσ* → CuIII LMCT transitions.Keywords
This publication has 67 references indexed in Scilit:
- Catalytic Phenol Hydroxylation with Dioxygen: Extension of the Tyrosinase Mechanism beyond the Protein MatrixAngewandte Chemie International Edition, 2013
- Bidentate guanidine ligands with ethylene spacer in copper-dioxygen chemistry: Structural characterization of bis(μ-hydroxo) dicopper complexesInorganica Chimica Acta, 2011
- Bis(μ-oxo) Dicopper(III) Species of the Simplest Peralkylated Diamine: Enhanced Reactivity toward Exogenous SubstratesInorganic Chemistry, 2010
- The First Catalytic Tyrosinase Model System Based on a Mononuclear Copper(I) Complex: Kinetics and MechanismAngewandte Chemie International Edition, 2010
- Copper/α-Ketocarboxylate Chemistry With Supporting Peralkylated Diamines: Reactivity of Copper(I) Complexes and Dicopper−Oxygen IntermediatesInorganic Chemistry, 2010
- Reaction Coordinate of a Functional Model of Tyrosinase: Spectroscopic and Computational CharacterizationJournal of the American Chemical Society, 2009
- Phenolate Hydroxylation in a Bis(μ-oxo)dicopper(III) Complex: Lessons from the Guanidine/Amine SeriesJournal of the American Chemical Society, 2009
- Reversible O−O Bond Cleavage in Copper−Dioxygen Isomers: Impact of Anion BasicityJournal of the American Chemical Society, 2006
- Structural and Electronic Differences of Copper(I) Complexes with Tris(pyrazolyl)methane and Hydrotris(pyrazolyl)borate LigandsInorganic Chemistry, 2006
- Multicopper Oxidases and OxygenasesChemical Reviews, 1996