Family of penta- and hexanuclear metallasilsesquioxanes: Synthesis, structure and catalytic properties in oxidations

Bilyachenko, Аlexey N.; Kulakova, Alena N.; Shul’pina, Lidia S.; Levitsky, Mikhail M.; Korlyukov, Alexander A.; Khrustalev, Victor N.; Zubavichus, Yan V.; Dorovatovskii, Pavel V.; Tsareva, Ul’yana S.; Shubina, Elena S.; Petrov, Аrtem А.; Vorontsov, N. V.; Shul’pin, Georgiy B.

doi:10.1016/j.jorganchem.2017.10.033

Cited by 25 publications

(24 citation statements)

References 46 publications

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“…This allowed us to isolate products of different nuclearity from two to nine, , , and different molecular topology. Sometimes, molecular topology and core nuclearity is governed by a promotive action of additional organic (P‐ or N‐based) ligands or solvent molecules intentionally introduced into the reaction medium. However, general regularities underlying the self‐assembly processes in this extremely complex system remain elusive, even though the total number of different CLMS structure types are rapidly increasing.…”

Section: Introductionmentioning

confidence: 99%

Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

et al. 2018

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Two prismatic phenyl-(PhSiO 1.5 ) 14 (CuO) 7 (1, 29 % yield) and methyl-(MeSiO 1.5 ) 14 (CuO) 7 (2, 19 % yield) heptacoppersilsesquioxanes were obtained by the interaction of Cu,Na-based cage silsesquioxanes [(RSiO 1.5 ) 12 (CuO) 4 (NaO 0.5 ) 4 ] (R = Ph, Me) with 4,4′-bipyridine and pyrazine, respectively, acting as "silent witness" ligands. Unusual molecular topologies of both compounds 1 and 2, which are the first representatives of [a] Nesmeyanov Institute of Organoelement Compounds,

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Section: Introductionmentioning

confidence: 99%

Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

et al. 2018

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“…10 For example, their high activity was reported for such reactions of high demand as olefin 11 or ringopening polymerization, 12 olefin epoxidation, 13 polycarbonate synthesis, 14 and a Meerwein−Ponndorf reaction, 15 as well as for hydroformylation. 16 In turn, our team reported on the catalytic activity of cagelike metallasilsesquioxanes in oxidative hydrocarbon functionalization 17 and amidation 18 reactions. Very recently, some of us presented the first example of the successful testing of CLMSs, including additional organic (phosphorusbased 19 ) ligands in such oxidative reactions.…”

Section: ■ Introductionmentioning

confidence: 99%

Si₁₀Cu₆N₄Cage Hexacoppersilsesquioxanes Containing N Ligands: Synthesis, Structure, and High Catalytic Activity in Peroxide Oxidations

et al. 2017

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The synthesis, composition, and catalytic properties of a new family of hexanuclear Cu(II)-based phenylsilsesquioxanes are described here. Structural studies of 17 synthesized compounds revealed the general principle underlying their molecular topology: viz., a central metal oxide layer consisting of two Cu trimers is coordinated by two cyclic [PhSiO] siloxanolate ligands to form a skewed sandwich architecture with the composition [(PhSiO)(CuO)]. In addition to this O ligation by the siloxanolate rings, two opposite copper ions are additionally coordinated by the nitrogen atoms of corresponding N ligand(s), such as 2,2'-bipyridine (compounds 1-9), 1,10-phenanthroline (compounds 10-13), mixed 1,10-phenanthroline/2,2'-bipyridine (compound 14), or bathophenanthroline (compounds 15-17). Finally, the charge balance is maintained by two HO (compounds 1-7, 10-13, and 15-17), two HCO (compound 8), or two CHCOO (compounds 9 and 14) anions. Complexes 1 and 10 exhibited a high activity in the oxidative amidation oxidation of alcohols. Compounds 1, 10, and 15 are very efficient homogeneous catalysts in the oxidation of alkanes and alcohols with peroxides.

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“…Mentioned above non-rigidity of siloxanolate ligands in the procedure of CLMS' assembly found additional evidence during the study of the synthesis of Cu-silsesquioxane in dimethylformamide (DMF) media (Scheme 1, complex 2). This reaction allows unprecedented pentanuclear CLMS 2 (PhSiO 1,5 ) 6 (PhSiO 1,5 ) 7 (HO 0.5 ) 2 (CuO) 5 (O 0.25 ) 2 (phen) 3 (Figure 2, top), which is very unlike pentacopper (PhSiO 1.5 ) 10 (CuO) 5 -CLMSs, reported earlier by us [54] and the Y. Kononevich team [52]. Most likely, this difference was due to the participation of phenanthroline ligands in the reaction reporting here.…”

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confidence: 56%

“…A ratio between interacting silanolate [(PhSiO 1.5 )(NaO 0.5 )] x and copper(II) chloride was oriented to let some amount of sodium ions not to be replaced by copper ions. The resulted Cu/Na mixture in the reaction system allowed us to expect a formation of an unusual cage product [11,12,[38][39][40], instead of widespread prismatic forms of Cu-only products [15,42,[52][53][54]. Indeed, this choice of ratio provokes the isolation of the nontrivial "double-ligated" Cu 4 Na 4 product 1 (Scheme 1, Figure 1).…”

Section: Description Of Compounds 1 Andmentioning

confidence: 99%

New Cu4Na4- and Cu5-Based Phenylsilsesquioxanes. Synthesis via Complexation with 1,10-Phenanthroline, Structures and High Catalytic Activity in Alkane Oxidations with Peroxides in Acetonitrile

et al. 2019

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Self-assembly of copper(II)phenylsilsesquioxane assisted by the use of 1,10-phenanthroline (phen) results in isolation of two unusual cage-like compounds: (PhSiO1,5)12(CuO)4(NaO0.5)4(phen)4 1 and (PhSiO1,5)6(PhSiO1,5)7(HO0.5)2(CuO)5(O0.25)2(phen)3 2. X-Ray diffraction study revealed extraordinaire molecular architectures of both products. Namely, complex 1 includes single cyclic (PhSiO1,5)12 silsesquioxane ligand. Four sodium ions of 1 are additionally ligated by 1,10-phenanthrolines. In turn, “sodium-less” complex 2 represents coordination of 1,10-phenanthrolines to copper ions. Two silsesquioxane ligands of 2 are: (i) noncondensed cubane of a rare Si6-type and (ii) unprecedented Si7-based ligand including two HOSiO1.5 fragments. These silanol units were formed due to removal of phenyl groups from silicon atoms, observed in mild conditions. The presence of phenanthroline ligands in products 1 and 2 favored the π–π stacking interactions between neighboring cages. Noticeable that in the case of 1 all four phenanthrolines participated in such supramolecular organization, unlike to complex 2 where one of the three phenanthrolines is not “supramolecularly active”. Complexes 1 and 2 were found to be very efficient precatalysts in oxidations with hydroperoxides. A new method for the determination of the participation of hydroxyl radicals has been developed.

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Family of penta- and hexanuclear metallasilsesquioxanes: Synthesis, structure and catalytic properties in oxidations

Cited by 25 publications

References 46 publications

Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Si₁₀Cu₆N₄Cage Hexacoppersilsesquioxanes Containing N Ligands: Synthesis, Structure, and High Catalytic Activity in Peroxide Oxidations

New Cu4Na4- and Cu5-Based Phenylsilsesquioxanes. Synthesis via Complexation with 1,10-Phenanthroline, Structures and High Catalytic Activity in Alkane Oxidations with Peroxides in Acetonitrile

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Family of penta- and hexanuclear metallasilsesquioxanes: Synthesis, structure and catalytic properties in oxidations

Cited by 25 publications

References 46 publications

Heptanuclear Cage CuII‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Heptanuclear Cage CuII‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Si10Cu6N4Cage Hexacoppersilsesquioxanes Containing N Ligands: Synthesis, Structure, and High Catalytic Activity in Peroxide Oxidations

New Cu4Na4- and Cu5-Based Phenylsilsesquioxanes. Synthesis via Complexation with 1,10-Phenanthroline, Structures and High Catalytic Activity in Alkane Oxidations with Peroxides in Acetonitrile

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Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Si₁₀Cu₆N₄Cage Hexacoppersilsesquioxanes Containing N Ligands: Synthesis, Structure, and High Catalytic Activity in Peroxide Oxidations