Copper(<scp>ii</scp>) 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

Choroba, Katarzyna; Kula, Sławomir; Raposo, Luís R.; Fernandes, Alexandra R.; Kruszyński, Rafał; Erfurt, Karol; Shul’pina, Lidia S.; Kozlov, Yuriy N.; Shul’pin, Georgiy B.

doi:10.1039/c9dt01922g

Cited by 50 publications

(31 citation statements)

References 136 publications

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“…The Cu(II) complexes of various terpyridines, equipped in 4′‐position with heteroaromatic rings, were utilized in the anaerobic oxidation of alkanes and secondary alcohols using H 2 O 2 and tert ‐butyl hydroperoxide (TBHP), as the respective oxidants . The oxidation of alkanes yields hydroperoxides as the primary products, which were – after reduction with PPh 3 – quantified by gas‐chromatographic analysis.…”

Section: Terpyridine Complexes As Catalysts For Organic Reactionsmentioning

confidence: 99%

Metal‐Terpyridine Complexes in Catalytic Application – A Spotlight on the Last Decade

Winter

Schubert

2020

ChemCatChem

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2,2′:6′,2′′‐Terpyridine (tpy) and its derivatives represent highly versatile ligands for the complexation of transition metal ions. Today, such complexes are employed in a highly diverse fashion – including inter alia materials science, opto‐electronics, pharmacy or catalysis. Concerning the latter one, a vast development has led to new or improved applications in both “conventional” organic chemistry (i. e., catalysis of functional‐group interconversions, CH‐activation or cross‐coupling reactions) as well as energy‐related applications (e. g., CO2 reduction, artificial photosynthesis, dye degradation). In this respect, not only homogeneous catalysts (i. e., molecular complexes) but also heterogeneous and recyclable ones have moved to the focus of interest. These heterogeneous structures include 1D metallopolymers, metal‐organic frameworks (MOFs), organic‐inorganic hybrids and bio‐inspired catalysts. We gave a first overview on this topic already in 2011; in here, the methods and implementations established within the last decade as well as relevant contributions from earlier works are presented and discussed.

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Section: Terpyridine Complexes As Catalysts For Organic Reactionsmentioning

confidence: 99%

Metal‐Terpyridine Complexes in Catalytic Application – A Spotlight on the Last Decade

Winter

Schubert

2020

ChemCatChem

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“…Substituted terpyridines such as 4 0 -chloro-2,2 0 :6 0 ,2 00 -terpyridine continue to be recognized as useful chelating ligands for many transition-metal ions, including platinum(II) (Qin et al, 2019), copper(II) (Choroba et al, 2019), cadmium(II) (Li et al, 2020), and zinc(II) (Li et al, 2019). Metal complexes containing zinc(II) and substituted terpyridines as chelating ligand have been shown to have promising antitumor activity (Liang et al, 2019).…”

Section: Structure Descriptionmentioning

confidence: 99%

Chlorido(4′-chloro-2,2′:6′,2′′-terpyridine-κ³ N,N′,N′′)(trifluoromethanesulfonato-κO)zinc(II) acetonitrile monosolvate

Adrian

Arman

2020

IUCr Data

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In the title complex, [Zn(CF3O3S)Cl(C15H10ClN3)]·CH3CN, the zinc(II) core is fivefold coordinated by one chloride, one trifluoromethanesulfonate O atom and three terpyridine N atoms in a slightly distorted square-pyramidal geometry. The structure provides a distinct example amongst other zinc(II) 4-chloroterpyridine complexes because of the unusual planarity of the coordinated chloride, the short length of the Zn—N bond opposite to the chloride ligand [1.9572 (15) Å], and the presence of an elongated Zn—O bond [2.3911 (14) Å] in the coordinated trifluoromethanesulfonate ion. A molecule of acetonitrile is also found in the asymmetric unit of the title complex.

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“…Machura et al [79] described the oxidation of inert alkanes to alkyl hydroperoxides by H2O2 catalyzed with monomeric oxovanadium(V) complexes of 8-hydroxyquinoline derivatives as noninnocent ligands (Scheme 4). The analogous ligands in complexes with copper or rhenium were used in oxidations by peroxides [80][81][82][83] Gushchin, Kuznetsov, et al recently [84,85] observed high activity among the vanadium complexes shown in Scheme 5 in the oxidation of hydrocarbons with peroxides. The mechanism for the generation of OH radicals is presented in Scheme 6.…”

Section: Oxidation Of Hydrocarbons and Alcohols With Peroxides Catalymentioning

confidence: 99%

“…Machura et al [79] described the oxidation of inert alkanes to alkyl hydroperoxides by H2O2 catalyzed with monomeric oxovanadium(V) complexes of 8-hydroxyquinoline derivatives as noninnocent ligands (Scheme 4). The analogous ligands in complexes with copper or rhenium were used in oxidations by peroxides [80][81][82][83] Scheme 4. Cleavage of the HO-OH bond and intramolecular electron transfer in a vanadium complex in the absence of PCA.…”

Section: Oxidation Of Hydrocarbons and Alcohols With Peroxides Catalymentioning

confidence: 99%

Metal Complexes Containing Redox-Active Ligands in Oxidation of Hydrocarbons and Alcohols: A Review

2019

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Ligands are innocent when they allow oxidation states of the central atoms to be defined. A noninnocent (or redox) ligand is a ligand in a metal complex where the oxidation state is not clear. Dioxygen can be a noninnocent species, since it exists in two oxidation states, i.e., superoxide (O2−) and peroxide (O22−). This review is devoted to oxidations of C–H compounds (saturated and aromatic hydrocarbons) and alcohols with peroxides (hydrogen peroxide, tert-butyl hydroperoxide) catalyzed by complexes of transition and nontransition metals containing innocent and noninnocent ligands. In many cases, the oxidation is induced by hydroxyl radicals. The mechanisms of the formation of hydroxyl radicals from H2O2 under the action of transition (iron, copper, vanadium, rhenium, etc.) and nontransition (aluminum, gallium, bismuth, etc.) metal ions are discussed. It has been demonstrated that the participation of the second hydrogen peroxide molecule leads to the rapture of O–O bond, and, as a result, to the facilitation of hydroxyl radical generation. The oxidation of alkanes induced by hydroxyl radicals leads to the formation of relatively unstable alkyl hydroperoxides. The data on regioselectivity in alkane oxidation allowed us to identify an oxidizing species generated in the decomposition of hydrogen peroxide: (hydroxyl radical or another species). The values of the ratio-of-rate constants of the interaction between an oxidizing species and solvent acetonitrile or alkane gives either the kinetic support for the nature of the oxidizing species or establishes the mechanism of the induction of oxidation catalyzed by a concrete compound. In the case of a bulky catalyst molecule, the ratio of hydroxyl radical attack rates upon the acetonitrile molecule and alkane becomes higher. This can be expanded if we assume that the reactions of hydroxyl radicals occur in a cavity inside a voluminous catalyst molecule, where the ratio of the local concentrations of acetonitrile and alkane is higher than in the whole reaction volume. The works of the authors of this review in this field are described in more detail herein.

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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

Abstract: The toxicity of six new Cu(ii) complexes was evaluated in cancer derived cell lines. A model of competitive interaction of hydroxyl radicals with CH3CN and RH in the catalyst cavity has been proposed.

Cited by 50 publications

References 136 publications

Metal‐Terpyridine Complexes in Catalytic Application – A Spotlight on the Last Decade

Metal‐Terpyridine Complexes in Catalytic Application – A Spotlight on the Last Decade

Chlorido(4′-chloro-2,2′:6′,2′′-terpyridine-κ³ N,N′,N′′)(trifluoromethanesulfonato-κO)zinc(II) acetonitrile monosolvate

Metal Complexes Containing Redox-Active Ligands in Oxidation of Hydrocarbons and Alcohols: A Review

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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

Abstract: The toxicity of six new Cu(ii) complexes was evaluated in cancer derived cell lines. A model of competitive interaction of hydroxyl radicals with CH3CN and RH in the catalyst cavity has been proposed.

Cited by 50 publications

References 136 publications

Metal‐Terpyridine Complexes in Catalytic Application – A Spotlight on the Last Decade

Metal‐Terpyridine Complexes in Catalytic Application – A Spotlight on the Last Decade

Chlorido(4′-chloro-2,2′:6′,2′′-terpyridine-κ3 N,N′,N′′)(trifluoromethanesulfonato-κO)zinc(II) acetonitrile monosolvate

Metal Complexes Containing Redox-Active Ligands in Oxidation of Hydrocarbons and Alcohols: A Review

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Chlorido(4′-chloro-2,2′:6′,2′′-terpyridine-κ³ N,N′,N′′)(trifluoromethanesulfonato-κO)zinc(II) acetonitrile monosolvate