A Co(III)-peroxo-arylboronate complex formed by nucleophilic reaction of a Co(III)-peroxo species

J Inorg Biochem. 2024 Apr 9;256:112552. doi: 10.1016/j.jinorgbio.2024.112552. Online ahead of print.ABSTRACTIn this work, we report the generation and characterization of two new Co(III)-peroxo complexes 2 and 3. 2 is best described as a mononuclear CoIII-(O2) complex that exhibits an 18O-isotope sensitive OO bond stretching vibration at 845(-49) cm-1, indicating a relatively weak peroxo moiety compared to those of other CoIII-(O2) complexes reported previously. Complex 3 is a CoIII-peroxo-arylboronate species having a rare {CoIIIOOBO} five-membered metallocycle, which is structurally characterized using X-ray crystallography. Investigations of the reaction mechanism using density functional theory calculations show that 2 likely undergoes a nucleophilic attack to an arylboronic acid, which is generated by hydrolysis of the BPh4- anion in wet acetonitrile solution, to first form a CoIII-peroxo-arylboronic acid adduct, followed by the loss of one benzene molecule to generate the five-membered metallocycle. The entire reaction is thermodynamically favorable. Taken together, the conversion of 2 to 3 represents the discovery of a novel nucleophilic reactivity that can be carried out by mononuclear Co(III)-peroxo complexes.PMID:38608554 | DOI:10.1016/j.jinorgbio.2024.112552

Source: Journal of Inorganic Biochemistry - April 12, 2024 Category: Biochemistry Authors: Yan Li Suhashini Handunneththige Wenting He Marat R Talipov Dong Wang Source Type: research