{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,11]],"date-time":"2026-09-11T02:42:29Z","timestamp":1789094549236,"version":"build-2803163510"},"reference-count":97,"publisher":"MDPI AG","issue":"23","license":[{"start":{"date-parts":[[2022,12,3]],"date-time":"2022-12-03T00:00:00Z","timestamp":1670025600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Russian Science Foundation","award":["22-13-00250"],"award-info":[{"award-number":["22-13-00250"]}]},{"name":"Russian Science Foundation","award":["370\/20"],"award-info":[{"award-number":["370\/20"]}]},{"name":"ISF (Israel Science Foundation)","award":["22-13-00250"],"award-info":[{"award-number":["22-13-00250"]}]},{"name":"ISF (Israel Science Foundation)","award":["370\/20"],"award-info":[{"award-number":["370\/20"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>A series of phenylsilsesquioxane-benzoate heptacopper complexes 1\u20133 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 1. A unique multi-ligation of copper ions (from (i) silsesquioxane, (ii) benzoate, (iii) benzyl alcohol, (iv) pyridine, (v) dimethyl-formamide and (vi) water ligands) was found in 1. Directed self-assembly using benzoic acid as a reactant afforded complexes 2\u20133 with the same main structural features as for 1, namely heptanuclear core coordinated by (i) two distorted pentameric cyclic silsesquioxane and (ii) four benzoate ligands, but featuring other solvate surroundings. Complex 3 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 \u00b0C 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 n-heptane and methylcyclohexane, respectively, indicate the involvement of of hydroxyl radicals. Complex 3 exhibits a high activity in the oxidation of alcohols.<\/jats:p>","DOI":"10.3390\/molecules27238505","type":"journal-article","created":{"date-parts":[[2022,12,5]],"date-time":"2022-12-05T07:07:31Z","timestamp":1670224051000},"page":"8505","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":15,"title":["Hybrid Silsesquioxane\/Benzoate Cu7-Complexes: Synthesis, Unique Cage Structure, and Catalytic Activity"],"prefix":"10.3390","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-3136-3675","authenticated-orcid":false,"given":"Alexey N.","family":"Bilyachenko","sequence":"first","affiliation":[{"name":"A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia"},{"name":"Peoples\u2019 Friendship University of Russia (RUDN University), Miklukho-Maklay Str. 6, 117198 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8806-2975","authenticated-orcid":false,"given":"Victor N.","family":"Khrustalev","sequence":"additional","affiliation":[{"name":"Peoples\u2019 Friendship University of Russia (RUDN University), Miklukho-Maklay Str. 6, 117198 Moscow, Russia"},{"name":"Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences (RAS), Leninsky Prospect 47, 119991 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Evgenii I.","family":"Gutsul","sequence":"additional","affiliation":[{"name":"A. N. 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Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Pavel V.","family":"Dorovatovskii","sequence":"additional","affiliation":[{"name":"National Research Center \u201cKurchatov Institute\u201d, Akademika Kurchatova pl. 1, 123182 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dmitri","family":"Gelman","sequence":"additional","affiliation":[{"name":"Institute of Chemistry, Edmond J. Safra Campus, The Hebrew University of Jerusalem, Jerusalem 91904, Israel"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8057-3703","authenticated-orcid":false,"given":"Elena S.","family":"Shubina","sequence":"additional","affiliation":[{"name":"A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1448-9228","authenticated-orcid":false,"given":"Georgiy B.","family":"Shul\u2019pin","sequence":"additional","affiliation":[{"name":"Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Ulitsa Kosygina 4, 119991 Moscow, Russia"},{"name":"Chair of Chemistry and Physics, Plekhanov Russian University of Economics, Stremyannyi Pereulok, Dom 36, 117997 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2022,12,3]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"2205","DOI":"10.1021\/cr9500747","article-title":"Hetero- and Metallasiloxanes Derived from Silanediols, Disilanols, Silanetriols, and Trisilanols","volume":"96","author":"Murugavel","year":"1996","journal-title":"Chem. 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