Oxygen activation by copper complexes with an aromatic bis(guanidine) ligand

Combining the new aromatic bis(guanidine) ligand bis(tetramethylguanidino)toluene (TMG2tol) and different copper salts led to four new complexes. The molecular structures were analysed by X-ray diffraction. Three of the complexes are active for 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 dicopper bis-µ-oxido species was investigated at low temperatures up to 273 K by UV/Vis spectroscopy with a stopped-flow setup. The results showed that the Cu2O2 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.

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