Formation of Hybrid Guanidine‐Stabilized Bis(μ‐oxo)dicopper Cores in Solution: Electronic and Steric Perturbations. Issue 32 (22nd October 2015)

• Record Type: Journal Article
• Authors: Herres‐Pawlis, Sonja; Haase, Roxana; Verma, Pratik; Hoffmann, Alexander; Kang, Peng; Stack, T. Daniel P.
• Is Part Of: European journal of inorganic chemistry. Issue 32(2015)
• Page Start: 5426
• Page End: 5436
• Publication Date: 2015-10-22
• Subjects: Bioinorganic chemistry -- Enzyme models -- Copper -- Bridging ligands -- Density functional calculations; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201500884
• Languages: English
• ISSNs: 1434-1948

Abstract

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 formedO cores but also enhance inner‐sphere phenolate hydroxylation pathways. TD‐DFT analysis on selected guanidine‐amineO species suggest that the additional visible‐wavelength feature observed is a guanidine π* → Cu2 O2 LMCT, which appears along with the classic oxo‐σu * → Cu III and πσ * → Cu III LMCT transitions. Abstract : Variation of the substituents on each side of a hybrid bidentate ligand reveals that less sterically demanding amine and guanidine substituents increase not only the thermal stability of the formedO cores but also enhance inner‐sphere phenolate hydroxylation pathways.