title: Cage-like copper(II) silsesquioxanes: transmetalation reactions and structural, quantum chemical, and catalytic studies.
abstract: The transmetalation of bimetallic copper-sodium silsesquioxane cages, namely, [(PhSiO1.5 )10 (CuO)2 (NaO0.5 )2 ] ("Cooling Tower"; 1), [(PhSiO1.5 )12 (CuO)4 (NaO0.5 )4 ] ("Globule"; 2), and [(PhSiO1.5 )6 (CuO)4 (NaO0.5 )4 (PhSiO1.5 )6 ] ("Sandwich"; 3), resulted in the generation of three types of hexanuclear cylinder-like copper silsesqui- oxanes, [(PhSiO1.5 )12 (CuO)6 (C4 H9 OH)2 (C2 H5 OH)6 ] (4), [(PhSiO1.5 )12 (CuO)6 (C4 H8 O2 )4 (PhCN)2 (MeOH)4 ] (5), and [(PhSiO1.5 )12 (CuO)6 (NaCl)(C4 H8 O2 )12 (H2 O)2 ] (6). The products show a prominent "solvating system-structure" dependency, as determined by X-ray diffraction. Topological analysis of cages 1-6 was also performed. In addition, DFT theory was used to examine the structures of the Cooling Tower and Cylinder compounds, as well as the spin density distributions. Compounds 1, 2, and 5 were applied as catalysts for the direct oxidation of alcohols and amines into the corresponding amides. Compound 6 is an excellent catalyst in the oxidation reactions of benzene and alcohols.
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov str., 28, Moscow 119991 (Russia). bilyachenko@ineos.ac.ru.
authors.forename: Alexey N
authors.initials: AN
authors.lastname: Bilyachenko
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov str., 28, Moscow 119991 (Russia).
authors.forename: Marina S
authors.initials: MS
authors.lastname: Dronova
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov str., 28, Moscow 119991 (Russia).
authors.forename: Alexey I
authors.initials: AI
authors.lastname: Yalymov
authors.affiliation: Institut des Biomolécules Max Mousseron (IBMM), UMR 5247 CNRS-Université Montpellier-ENSCM, Bâtiment Chimie (17), Faculté des Sciences Place, Eugène Bataillon 34095 Montpellier cedex 5 (France). frederic.lamaty@univ-montp2.fr.
authors.forename: Frédéric
authors.initials: F
authors.lastname: Lamaty
authors.affiliation: Institut des Biomolécules Max Mousseron (IBMM), UMR 5247 CNRS-Université Montpellier-ENSCM, Bâtiment Chimie (17), Faculté des Sciences Place, Eugène Bataillon 34095 Montpellier cedex 5 (France).
authors.forename: Xavier
authors.initials: X
authors.lastname: Bantreil
authors.affiliation: Institut des Biomolécules Max Mousseron (IBMM), UMR 5247 CNRS-Université Montpellier-ENSCM, Bâtiment Chimie (17), Faculté des Sciences Place, Eugène Bataillon 34095 Montpellier cedex 5 (France).
authors.forename: Jean
authors.initials: J
authors.lastname: Martinez
authors.affiliation: Institut des Biomolécules Max Mousseron (IBMM), UMR 5247 CNRS-Université Montpellier-ENSCM, Bâtiment Chimie (17), Faculté des Sciences Place, Eugène Bataillon 34095 Montpellier cedex 5 (France).
authors.forename: Christelle
authors.initials: C
authors.lastname: Bizet
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov str., 28, Moscow 119991 (Russia).
authors.forename: Lidia S
authors.initials: LS
authors.lastname: Shul'pina
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov str., 28, Moscow 119991 (Russia). alex@xrlab.ineos.ac.ru.|Pirogov Russian National Research Medical University, Ostrovitianov str., 1, Moscow 117997 (Russia). alex@xrlab.ineos.ac.ru.
authors.forename: Alexander A
authors.initials: AA
authors.lastname: Korlyukov
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov str., 28, Moscow 119991 (Russia).
authors.forename: Dmitry E
authors.initials: DE
authors.lastname: Arkhipov
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov str., 28, Moscow 119991 (Russia). levitsk@ineos.ac.ru.
authors.forename: Mikhail M
authors.initials: MM
authors.lastname: Levitsky
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov str., 28, Moscow 119991 (Russia).
authors.forename: Elena S
authors.initials: ES
authors.lastname: Shubina
authors.affiliation: Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon (Portugal).
authors.forename: Alexander M
authors.initials: AM
authors.lastname: Kirillov
authors.affiliation: Semenov Institute of Chemical Physics, Russian Academy of Science ul. Kosygina, dom 4, Moscow 119991 (Russia). shulpin@chph.ras.ru.
authors.forename: Georgiy B
authors.initials: GB
authors.lastname: Shul'pin
mesh_terms: D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction
chemical_list: D003300:Copper
keywords: amidation; cage compounds; density functional calculations; metallacycles; oxidation