Anion effect on the cumene hydroperoxide decomposition in the presence of Cu(II) 1,10-phenanthrolinates

• Published in: Journal of organometallic chemistry Vol. 922; p. 121371
• Main Authors: Тurovskij, Nikolaj, Raksha, Elena, Berestneva, Yuliya, Eresko, Alexander
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.09.2020
• Subjects: 1,10-Phenanthroline; Anion effect; Catalysis; Catalytic decomposition; Cumene hydroperoxide; 1,10-Phenanthroline; Catalysis; Cumene hydroperoxide; Anion effect; Catalytic decomposition
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2020.121371

Kinetics of the cumene hydroperoxide catalytic decomposition in the presence of Cu(II) salt complexes with 1,10-phenanthroline (Phen) has been investigated in the water: ethanol (1:1) solvent mixture. Catalytic properties of Cu(CH3COO)2 - Phen complex were confirmed: after full hydroperoxide conversion its new portion had been added to the reaction mixture. The hydroperoxide decomposition rate constant observed on the second cycle was the same. The salt anion effect on the complex catalytic activity has been revealed. The rate constant of the cumene hydroperoxide catalytic decomposition increases in the following row of anions: SO42− < Cl− < CH3COO−, the hydroperoxide decomposition in the presence of Cu(II) nitrate in the same experimental conditions was not observed. The effect of the anion nature in the reaction of cumene hydroperoxide catalytic decomposition may be associated with both the structure of the Cu(II) complex with Phen, as well as the structure of the hydroperoxide - catalyst complex. In addition, the double activation effect is observed in the reaction considered. The hydroperoxide molecule is chemically activated by the corresponded Cu(ІІ) salt. The Cu(ІІ) salt reactivity by-turn is activated in the presence of 1,10-phenanthroline and can be regulated by means of variation in corresponded salt anion. [Display omitted] •Cu(II) 1,10-phenanthrolinates reactivity depends on the salt anion nature.•The effect of the anion nature may be associated with the catalyst structure.•The anion nature effect may be caused by hydroperoxide-catalyst complex structure.•The hydroperoxide is chemically activated by the corresponded Cu(ІІ) complex cation.