Oxygen Activation by Copper Complexes with an Aromatic Bis(guanidine) Ligand. Issue 27 (21st July 2017)

• Record Type: Journal Article
• Authors: Strassl, Florian; Grimm‐Lebsanft, Benjamin; Rukser, Dieter; Biebl, Florian; Biednov, Mykola; Brett, Calvin; Timmermann, Riccardo; Metz, Fabian; Hoffmann, Alexander; Rübhausen, Michael; Herres‐Pawlis, Sonja
• Is Part Of: European journal of inorganic chemistry. Issue 27(2017)
• Page Start: 3350
• Page End: 3359
• Publication Date: 2017-07-21
• Subjects: Copper -- N ligands -- Dioxygen -- Raman spectroscopy -- Density functional calculations; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201700528
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Combining the new aromatic bis(guanidine) ligand bis(tetramethylguanidino)toluene (TMG2 tol) and different copper salts led to four new complexes. The molecular structures were analysed by X‐ray diffraction. Three of the complexes are active in biomimetic activation of oxygen. It is the first time a bis‐µ‐oxido species of an aromatic guanidine copper complex is analysed by Raman and UV/Vis spectroscopy. The formation and decay of the bis(µ‐oxido)dicopper species were investigated at low temperatures up to 273 K by UV/Vis spectroscopy with a stopped‐flow setup. The results showed that the Cu2 O2 intermediate of an aromatic guanidine–copper complex decays much faster than most known bis(guanidine) complexes. Moreover, natural bond orbital (NBO) analyses revealed that the aromatic guanidine is the stronger donor compared to the aliphatic one. Abstract : The new aromatic bis(guanidine) ligand bis(tetramethylguanidino)toluene was combined with copper salts to achieve complexes that activate oxygen. It is the first time a bis(µ‐oxido) species of an aromatic guanidine–copper complex is analysed by Raman and UV/Vis spectroscopy as well as density functional theory (DFT).