A Novel Family of Cage-like (CuLi, CuNa, CuK)-phenylsilsesquioxane Complexes with 8-Hydroxyquinoline Ligands: Synthesis, Structure, and Catalytic Activity

Alexey N. Bilyachenko, Victor N. Khrustalev, Anna Y. Zueva, Ekaterina M. Titova, Grigorii S. Astakhov, Yan V. Zubavichus, Pavel V. Dorovatovskii, Alexander A. Korlyukov, Lidia S. Shul’pina, Elena S. Shubina, Yuriy N. Kozlov, Nikolay S. Ikonnikov, Dmitri Gelman, Georgiy B. Shul’pin

Research output: Contribution to journalArticlepeer-review

Abstract

The first examples of metallasilsesquioxane complexes, including ligands of the 8-hydroxyquinoline family 1–9, were synthesized, and their structures were established by single crystal X-ray diffraction using synchrotron radiation. Compounds 1–9 tend to form a type of sandwich-like cage of Cu4M2 nuclearity (M = Li, Na, K). Each complex includes two cisoid pentameric silsesquioxane ligands and two 8-hydroxyquinoline ligands. The latter coordinates the copper ions and corresponding alkaline metal ions (via the deprotonated oxygen site). A characteristic (size) of the alkaline metal ion and a variation of characteristics of nitrogen ligands (8-hydroxyquinoline vs. 5-chloro-8-hydroxyquinoline vs. 5,7-dibromo-8-hydroxyquinoline vs. 5,7-diiodo-8-hydroxyquinoline) are highly influential for the formation of the supramolecular structure of the complexes 3a, 5, and 7–9. The Cu6Na2-based compound 2 exhibits high catalytic activity towards the oxidation of (i) hydrocarbons by H2O2 activated with HNO3, and (ii) alcohols by tert-butyl hydroperoxide. Studies of kinetics and their selectivity has led us to conclude that it is the hydroxyl radicals that play a crucial role in this process.

Original languageAmerican English
Article number6205
JournalMolecules
Volume27
Issue number19
DOIs
StatePublished - Oct 2022

Keywords

  • 8-hydroxyquinoline ligands
  • alkanes
  • alkyl hydroperoxide
  • cage-like compounds
  • coordination polymers
  • half-sandwich units
  • metallasilsesquioxanes
  • oxidative catalysis

All Science Journal Classification (ASJC) codes

  • Drug Discovery
  • Analytical Chemistry
  • Chemistry (miscellaneous)
  • Molecular Medicine
  • Physical and Theoretical Chemistry
  • Pharmaceutical Science
  • Organic Chemistry

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