Copper(ii) complexes with 2,2':6',2''-terpyridine, 2,6-di(thiazol-2-yl)pyridine and 2,6-di(pyrazin-2-yl)pyridine substituted with quinolines. Synthesis, structure, antiproliferative activity, and catalytic activity in the oxidation of alkanes and alcohols with peroxides

Katarzyna Choroba; Barbara Machura; Slawomir Kula; Luis R Raposo; Alexandra R Fernandes; Rafal Kruszynski; Karol Erfurt; Lidia S Shul'pina; Yuriy N Kozlov; Georgiy B Shul'pin

doi:10.1039/c9dt01922g

Copper(ii) complexes with 2,2':6',2''-terpyridine, 2,6-di(thiazol-2-yl)pyridine and 2,6-di(pyrazin-2-yl)pyridine substituted with quinolines. Synthesis, structure, antiproliferative activity, and catalytic activity in the oxidation of alkanes and alcohols with peroxides

Dalton Trans. 2019 Sep 7;48(33):12656-12673. doi: 10.1039/c9dt01922g. Epub 2019 Aug 6.

Affiliations

¹ Institute of Chemistry, University of Silesia, Szkolna 9, 40-006 Katowice, Poland. bmachura@poczta.onet.pl.
² UCIBIO, Departamento de Ciências da Vida, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, Campus de Caparica, 2829-516 Caparica, Portugal. ma.fernandes@fct.unl.pt.
³ Institute of General and Ecological Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924 Lodz, Poland.
⁴ Department of Chemical Organic Technology and Petrochemistry, Silesian University of Technology, Krzywoustego 4, 44-100 Gliwice, Poland.
⁵ Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ulitsa Vavilova, dom 28, Moscow 119991, Russia.
⁶ Semenov Institute of Chemical Physics, Russian Academy of Sciences, ulitsa Kosygina, dom 4, Moscow 119991, Russia. shulpin@chph.ras.ru and Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ulitsa Vavilova, dom 28, Moscow 119991, Russia.
⁷ Semenov Institute of Chemical Physics, Russian Academy of Sciences, ulitsa Kosygina, dom 4, Moscow 119991, Russia. shulpin@chph.ras.ru and Plekhanov Russian University of Economics, Stremyannyi pereulok, dom 36, Moscow 117997, Russia and People's Friendship University of Russia, ul. Miklukho-Maklaya, dom 6, Moscow 117198, Russia.

PMID: 31384866
DOI: 10.1039/c9dt01922g

Abstract

A series of 2,2':6',2''-terpyridine (terpy), 2,6-di(thiazol-2-yl)pyridine (dtpy) and 2,6-di(pyrazin-2-yl)pyridine (dppy) derivatives with n-quinolyl substituents (n = 2 and 4) was used to synthesize five-coordinate complexes [CuCl₂(n-quinolyl-terpy)] (1-2), [CuCl₂(n-quinolyl-dtpy)] (3-4) and [CuCl₂(n-quinolyl-dppy)] (5-6), respectively. The main emphasis of the research was to investigate the impact of the triimine skeleton (terpy, dtpy and dppy) and n-quinolyl pendant substituent on the antiproliferative and catalytic properties of 1-6. The obtained Cu(ii) compounds were studied as antiproliferative agents against human colorectal (HCT116) and ovarian (A2780) carcinoma, and they were used as catalysts for the oxidation of alkanes and alcohols with peroxides under mild conditions. The kinetic characteristics of the oxidizing species generated by the catalytic system Cu(ii) complex-H₂O₂ in CH₃CN were obtained from the dependence of the alkane oxidation rate on its initial concentration. A model of competitive interaction of hydroxyl radicals with CH₃CN and RH in the catalyst cavity has been proposed which is based on the simultaneous study of kinetics and selectivity in alkane oxidations.