Hybrid Silsesquioxane/Benzoate Cu<sub>7</sub>-Complexes: Synthesis, Unique Cage Structure, and Catalytic Activity
A series of phenylsilsesquioxane-benzoate heptacopper complexes <b>1</b>–<b>3</b> were synthesized and characterized by X-ray crystallography. Two parallel routes of toluene spontaneous oxidation (into benzyl alcohol and benzoate) assisted the formation of the cagelike struct...
| Main Authors: | , , , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2022-12-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/27/23/8505 |
| _version_ | 1827642853254234112 |
|---|---|
| author | Alexey N. Bilyachenko Victor N. Khrustalev Evgenii I. Gutsul Anna Y. Zueva Alexander A. Korlyukov Lidia S. Shul’pina Nikolay S. Ikonnikov Pavel V. Dorovatovskii Dmitri Gelman Elena S. Shubina Georgiy B. Shul’pin |
| author_facet | Alexey N. Bilyachenko Victor N. Khrustalev Evgenii I. Gutsul Anna Y. Zueva Alexander A. Korlyukov Lidia S. Shul’pina Nikolay S. Ikonnikov Pavel V. Dorovatovskii Dmitri Gelman Elena S. Shubina Georgiy B. Shul’pin |
| author_sort | Alexey N. Bilyachenko |
| collection | DOAJ |
| description | A series of phenylsilsesquioxane-benzoate heptacopper complexes <b>1</b>–<b>3</b> were synthesized and characterized by X-ray crystallography. Two parallel routes of toluene spontaneous oxidation (into benzyl alcohol and benzoate) assisted the formation of the cagelike structure <b>1</b>. A unique multi-ligation of copper ions (from (<i>i</i>) silsesquioxane, (<i>ii</i>) benzoate, (<i>iii</i>) benzyl alcohol, (<i>iv</i>) pyridine, (<i>v</i>) dimethyl-formamide and (<i>vi</i>) water ligands) was found in <b>1</b>. Directed self-assembly using benzoic acid as a reactant afforded complexes <b>2</b>–<b>3</b> with the same main structural features as for <b>1</b>, namely heptanuclear core coordinated by (<i>i</i>) two distorted pentameric cyclic silsesquioxane and (<i>ii</i>) four benzoate ligands, but featuring other solvate surroundings. Complex <b>3</b> was evaluated as a catalyst for the oxidation of alkanes to alkyl hydroperoxides and alcohols to ketones with hydrogen peroxide and tert-butyl hydroperoxide, respectively, at 50 °C in acetonitrile. The maximum yield of cyclohexane oxidation products as high as 32% was attained. The oxidation reaction results in a mixture of cyclohexyl hydroperoxide, cyclohexanol, and cyclohexanone. Upon the addition of triphenylphosphine, the cyclohexyl hydroperoxide is completely converted to cyclohexanol. The specific regio- and chemoselectivity in the oxidation of <i>n</i>-heptane and methylcyclohexane, respectively, indicate the involvement of of hydroxyl radicals. Complex <b>3</b> exhibits a high activity in the oxidation of alcohols. |
| first_indexed | 2024-03-09T17:38:46Z |
| format | Article |
| id | doaj.art-7a9b1b45b92f44ceb434853ecc55d5e5 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T17:38:46Z |
| publishDate | 2022-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-7a9b1b45b92f44ceb434853ecc55d5e52023-11-24T11:43:21ZengMDPI AGMolecules1420-30492022-12-012723850510.3390/molecules27238505Hybrid Silsesquioxane/Benzoate Cu<sub>7</sub>-Complexes: Synthesis, Unique Cage Structure, and Catalytic ActivityAlexey N. Bilyachenko0Victor N. Khrustalev1Evgenii I. Gutsul2Anna Y. Zueva3Alexander A. Korlyukov4Lidia S. Shul’pina5Nikolay S. Ikonnikov6Pavel V. Dorovatovskii7Dmitri Gelman8Elena S. Shubina9Georgiy B. Shul’pin10A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, RussiaPeoples’ Friendship University of Russia (RUDN University), Miklukho-Maklay Str. 6, 117198 Moscow, RussiaA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, RussiaPeoples’ Friendship University of Russia (RUDN University), Miklukho-Maklay Str. 6, 117198 Moscow, RussiaA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, RussiaA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, RussiaA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, RussiaNational Research Center “Kurchatov Institute”, Akademika Kurchatova pl. 1, 123182 Moscow, RussiaInstitute of Chemistry, Edmond J. Safra Campus, The Hebrew University of Jerusalem, Jerusalem 91904, IsraelA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, RussiaSemenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Ulitsa Kosygina 4, 119991 Moscow, RussiaA series of phenylsilsesquioxane-benzoate heptacopper complexes <b>1</b>–<b>3</b> were synthesized and characterized by X-ray crystallography. Two parallel routes of toluene spontaneous oxidation (into benzyl alcohol and benzoate) assisted the formation of the cagelike structure <b>1</b>. A unique multi-ligation of copper ions (from (<i>i</i>) silsesquioxane, (<i>ii</i>) benzoate, (<i>iii</i>) benzyl alcohol, (<i>iv</i>) pyridine, (<i>v</i>) dimethyl-formamide and (<i>vi</i>) water ligands) was found in <b>1</b>. Directed self-assembly using benzoic acid as a reactant afforded complexes <b>2</b>–<b>3</b> with the same main structural features as for <b>1</b>, namely heptanuclear core coordinated by (<i>i</i>) two distorted pentameric cyclic silsesquioxane and (<i>ii</i>) four benzoate ligands, but featuring other solvate surroundings. Complex <b>3</b> was evaluated as a catalyst for the oxidation of alkanes to alkyl hydroperoxides and alcohols to ketones with hydrogen peroxide and tert-butyl hydroperoxide, respectively, at 50 °C in acetonitrile. The maximum yield of cyclohexane oxidation products as high as 32% was attained. The oxidation reaction results in a mixture of cyclohexyl hydroperoxide, cyclohexanol, and cyclohexanone. Upon the addition of triphenylphosphine, the cyclohexyl hydroperoxide is completely converted to cyclohexanol. The specific regio- and chemoselectivity in the oxidation of <i>n</i>-heptane and methylcyclohexane, respectively, indicate the involvement of of hydroxyl radicals. Complex <b>3</b> exhibits a high activity in the oxidation of alcohols.https://www.mdpi.com/1420-3049/27/23/8505metallasilsesquioxanescagelike compoundsbenzoate ligandsoxidative catalysisalkanesalkyl hydroperoxide |
| spellingShingle | Alexey N. Bilyachenko Victor N. Khrustalev Evgenii I. Gutsul Anna Y. Zueva Alexander A. Korlyukov Lidia S. Shul’pina Nikolay S. Ikonnikov Pavel V. Dorovatovskii Dmitri Gelman Elena S. Shubina Georgiy B. Shul’pin Hybrid Silsesquioxane/Benzoate Cu<sub>7</sub>-Complexes: Synthesis, Unique Cage Structure, and Catalytic Activity Molecules metallasilsesquioxanes cagelike compounds benzoate ligands oxidative catalysis alkanes alkyl hydroperoxide |
| title | Hybrid Silsesquioxane/Benzoate Cu<sub>7</sub>-Complexes: Synthesis, Unique Cage Structure, and Catalytic Activity |
| title_full | Hybrid Silsesquioxane/Benzoate Cu<sub>7</sub>-Complexes: Synthesis, Unique Cage Structure, and Catalytic Activity |
| title_fullStr | Hybrid Silsesquioxane/Benzoate Cu<sub>7</sub>-Complexes: Synthesis, Unique Cage Structure, and Catalytic Activity |
| title_full_unstemmed | Hybrid Silsesquioxane/Benzoate Cu<sub>7</sub>-Complexes: Synthesis, Unique Cage Structure, and Catalytic Activity |
| title_short | Hybrid Silsesquioxane/Benzoate Cu<sub>7</sub>-Complexes: Synthesis, Unique Cage Structure, and Catalytic Activity |
| title_sort | hybrid silsesquioxane benzoate cu sub 7 sub complexes synthesis unique cage structure and catalytic activity |
| topic | metallasilsesquioxanes cagelike compounds benzoate ligands oxidative catalysis alkanes alkyl hydroperoxide |
| url | https://www.mdpi.com/1420-3049/27/23/8505 |
| work_keys_str_mv | AT alexeynbilyachenko hybridsilsesquioxanebenzoatecusub7subcomplexessynthesisuniquecagestructureandcatalyticactivity AT victornkhrustalev hybridsilsesquioxanebenzoatecusub7subcomplexessynthesisuniquecagestructureandcatalyticactivity AT evgeniiigutsul hybridsilsesquioxanebenzoatecusub7subcomplexessynthesisuniquecagestructureandcatalyticactivity AT annayzueva hybridsilsesquioxanebenzoatecusub7subcomplexessynthesisuniquecagestructureandcatalyticactivity AT alexanderakorlyukov hybridsilsesquioxanebenzoatecusub7subcomplexessynthesisuniquecagestructureandcatalyticactivity AT lidiasshulpina hybridsilsesquioxanebenzoatecusub7subcomplexessynthesisuniquecagestructureandcatalyticactivity AT nikolaysikonnikov hybridsilsesquioxanebenzoatecusub7subcomplexessynthesisuniquecagestructureandcatalyticactivity AT pavelvdorovatovskii hybridsilsesquioxanebenzoatecusub7subcomplexessynthesisuniquecagestructureandcatalyticactivity AT dmitrigelman hybridsilsesquioxanebenzoatecusub7subcomplexessynthesisuniquecagestructureandcatalyticactivity AT elenasshubina hybridsilsesquioxanebenzoatecusub7subcomplexessynthesisuniquecagestructureandcatalyticactivity AT georgiybshulpin hybridsilsesquioxanebenzoatecusub7subcomplexessynthesisuniquecagestructureandcatalyticactivity |