CATALYSIS OF HYDRODEHALOGENATION REACTION OF HALOARENES BY CARBENE PEPPSI-PALLADIUM COMPLEXES
The synthesis of a number of carbene PEPPSI-complexes of palladium with various pyridine and carbene ligands was carried out by reactions of 1,3-bis-(2,6-dibenzhydryl-4-methylphenyl)imidazolium chloride IPr*.HCl [compounds 7a-c IPr*PdCl2L’, L’ = pyridine (а), 3-chloropyridine (b), 4-dimethylaminopy...
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2022
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oai:ojs2.1444248.nisspano.web.hosting-test.net:article-4012022-02-22T11:29:28Z CATALYSIS OF HYDRODEHALOGENATION REACTION OF HALOARENES BY CARBENE PEPPSI-PALLADIUM COMPLEXES Saberov , Vagiz Avksentiev, Alexander Rayenko, Gennady Ryabitsky , Alexey Yenya , Vasil Nechitaylov , Maxim Korotkikh , Nikolai Carbene complexes, PEPPSI, catalysis, haloarene hydrodehalogenation. The synthesis of a number of carbene PEPPSI-complexes of palladium with various pyridine and carbene ligands was carried out by reactions of 1,3-bis-(2,6-dibenzhydryl-4-methylphenyl)imidazolium chloride IPr*.HCl [compounds 7a-c IPr*PdCl2L’, L’ = pyridine (а), 3-chloropyridine (b), 4-dimethylaminopyridine (с)], 1,3-bis-(2,6-diisopropylphenyl)imidazolium perchlorate IPr.HClO4 [compounds 8a,b IPr.PdCl2L’, L’ = 3-chloropyridine (а), о-phenanthroline (b)], 1,3-diphenyl-4-(2,6-diisopropylphenyl)-1,2,4-triazolium perchlorate L.HClO4 (complex 9 LPdCl2L’, L’ = 3-chloropyridine) and 1,3-dicetylimidazolium bromide L.HBr (complex 11 LPdCl2L’, L’ = pyridine) with palladium chloride in pyridines (pyridine, 3-chloropyridine), or acetonitrile in the presence of potassium carbonate. Yields of compounds – from high (56–100%) to moderate (36 %). The structure of the compounds was confirmed by 1H and 13C NMR spectroscopy. Chemical shifts of carbene atoms in the 13C NMR spectra of complexes 7a-c. 8a, b 11 are in the region 151.0-156.2 ppm, for complex 9 - at 174.4 ppm A high catalytic effect of sterically shielded complexes 7a, b, 8a, b in the hydrodehalogenation reaction of p-dichlorobenzene and hexachlorobenzene under the action of potassium tert-butoxide in isopropanol was established. 1,3-Bis-(2,6-dibenzhydryl-4-methylphenyl)-imidazol-2-ylidene complexes 7a, b (quantitative conversions with p-dichlorobenzene are achieved with 0.013 mol% of catalyst) show the highest efficiency, but the compound with 4-dimethylaminopyridine ligand 7c has significantly lower efficiency (22% conversion under these conditions). Complexes with 1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene ligand 8a, b are close in efficiency to compounds 7a, b (for 7a quantitative conversion is achieved with 0.026 mol% of catalyst). Phenanthroline-containing complex 8b is less effective than complex 8a (87% conversion with 0.052 mol% of catalyst). Complex 9 is much less effective (even with 0.13 mol% of catalyst 13% conversion is achieved). Compound 11 catalyzes the reaction well only when the amount of catalyst is up to 1.3 mol% (98% conversion). Thus, compounds 7a, b, 8a are the best PEPPSI-catalysts for hydrodehalogenation of haloarenes promising for industrial decontamination of persistent organic pollutants (hexachlorobenzene, DDT, dioxins and polychlorinated biphenyls, etc.). V.I.Vernadsky Institute of General and Inorganic Chemistry 2022-02-16 Article Article Organic chemistry Органическая xимия Органічна xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/401 10.33609/2708-129X.88.01.2022.67-81 Ukrainian Chemistry Journal; Vol. 88 No. 1 (2022): Ukrainian Chemistry Journal; 67-81 Украинский химический журнал; Том 88 № 1 (2022): Ukrainian Chemistry Journal; 67-81 Український хімічний журнал; Том 88 № 1 (2022): Український хімічний журнал; 67-81 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/401/212 |
| institution |
Ukrainian Chemistry Journal |
| baseUrl_str |
|
| datestamp_date |
2022-02-22T11:29:28Z |
| collection |
OJS |
| language |
English |
| topic_facet |
Carbene complexes PEPPSI catalysis haloarene hydrodehalogenation. |
| format |
Article |
| author |
Saberov , Vagiz Avksentiev, Alexander Rayenko, Gennady Ryabitsky , Alexey Yenya , Vasil Nechitaylov , Maxim Korotkikh , Nikolai |
| spellingShingle |
Saberov , Vagiz Avksentiev, Alexander Rayenko, Gennady Ryabitsky , Alexey Yenya , Vasil Nechitaylov , Maxim Korotkikh , Nikolai CATALYSIS OF HYDRODEHALOGENATION REACTION OF HALOARENES BY CARBENE PEPPSI-PALLADIUM COMPLEXES |
| author_facet |
Saberov , Vagiz Avksentiev, Alexander Rayenko, Gennady Ryabitsky , Alexey Yenya , Vasil Nechitaylov , Maxim Korotkikh , Nikolai |
| author_sort |
Saberov , Vagiz |
| title |
CATALYSIS OF HYDRODEHALOGENATION REACTION OF HALOARENES BY CARBENE PEPPSI-PALLADIUM COMPLEXES |
| title_short |
CATALYSIS OF HYDRODEHALOGENATION REACTION OF HALOARENES BY CARBENE PEPPSI-PALLADIUM COMPLEXES |
| title_full |
CATALYSIS OF HYDRODEHALOGENATION REACTION OF HALOARENES BY CARBENE PEPPSI-PALLADIUM COMPLEXES |
| title_fullStr |
CATALYSIS OF HYDRODEHALOGENATION REACTION OF HALOARENES BY CARBENE PEPPSI-PALLADIUM COMPLEXES |
| title_full_unstemmed |
CATALYSIS OF HYDRODEHALOGENATION REACTION OF HALOARENES BY CARBENE PEPPSI-PALLADIUM COMPLEXES |
| title_sort |
catalysis of hydrodehalogenation reaction of haloarenes by carbene peppsi-palladium complexes |
| description |
The synthesis of a number of carbene PEPPSI-complexes of palladium with various pyridine and carbene ligands was carried out by reactions of 1,3-bis-(2,6-dibenzhydryl-4-methylphenyl)imidazolium chloride IPr*.HCl [compounds 7a-c IPr*PdCl2L’, L’ = pyridine (а), 3-chloropyridine (b), 4-dimethylaminopyridine (с)], 1,3-bis-(2,6-diisopropylphenyl)imidazolium perchlorate IPr.HClO4 [compounds 8a,b IPr.PdCl2L’, L’ = 3-chloropyridine (а), о-phenanthroline (b)], 1,3-diphenyl-4-(2,6-diisopropylphenyl)-1,2,4-triazolium perchlorate L.HClO4 (complex 9 LPdCl2L’, L’ = 3-chloropyridine) and 1,3-dicetylimidazolium bromide L.HBr (complex 11 LPdCl2L’, L’ = pyridine) with palladium chloride in pyridines (pyridine, 3-chloropyridine), or acetonitrile in the presence of potassium carbonate. Yields of compounds – from high (56–100%) to moderate (36 %). The structure of the compounds was confirmed by 1H and 13C NMR spectroscopy. Chemical shifts of carbene atoms in the 13C NMR spectra of complexes 7a-c. 8a, b 11 are in the region 151.0-156.2 ppm, for complex 9 - at 174.4 ppm A high catalytic effect of sterically shielded complexes 7a, b, 8a, b in the hydrodehalogenation reaction of p-dichlorobenzene and hexachlorobenzene under the action of potassium tert-butoxide in isopropanol was established. 1,3-Bis-(2,6-dibenzhydryl-4-methylphenyl)-imidazol-2-ylidene complexes 7a, b (quantitative conversions with p-dichlorobenzene are achieved with 0.013 mol% of catalyst) show the highest efficiency, but the compound with 4-dimethylaminopyridine ligand 7c has significantly lower efficiency (22% conversion under these conditions). Complexes with 1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene ligand 8a, b are close in efficiency to compounds 7a, b (for 7a quantitative conversion is achieved with 0.026 mol% of catalyst). Phenanthroline-containing complex 8b is less effective than complex 8a (87% conversion with 0.052 mol% of catalyst). Complex 9 is much less effective (even with 0.13 mol% of catalyst 13% conversion is achieved). Compound 11 catalyzes the reaction well only when the amount of catalyst is up to 1.3 mol% (98% conversion). Thus, compounds 7a, b, 8a are the best PEPPSI-catalysts for hydrodehalogenation of haloarenes promising for industrial decontamination of persistent organic pollutants (hexachlorobenzene, DDT, dioxins and polychlorinated biphenyls, etc.). |
| publisher |
V.I.Vernadsky Institute of General and Inorganic Chemistry |
| publishDate |
2022 |
| url |
https://ucj.org.ua/index.php/journal/article/view/401 |
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| first_indexed |
2025-09-24T17:43:43Z |
| last_indexed |
2025-09-24T17:43:43Z |
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