Heptanuclear Cage Cu<sup>II</sup>‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Bilyachenko, Аlexey N.; Levitsky, Mikhail M.; Korlyukov, Alexander A.; Khrustalev, Victor N.; Zubavichus, Yan V.; Shul’pina, Lidia S.; Shubina, Elena S.; Вологжанина, Анна В.; Shul’pin, Georgiy B.

doi:10.1002/ejic.201701340

Cited by 27 publications

(27 citation statements)

References 69 publications

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“…It should be noted that in Ref. [81] (Figure 12), the complexes 18 and 19 used in the catalysis of alkane oxidation exhibited somewhat different activity. Compound 18 gave a higher yield of oxidation products.…”

Section: Oxidation Catalyzed By Copper Complexesmentioning

confidence: 91%

“…First examples of heptanuclear cage silsesquioxanes, (PhSiO1.5)14(CuO)7 18 and (Me-SiO1.5)14(CuO)7 19, were obtained [81]. It should be noted that in Ref.…”

Section: Oxidation Catalyzed By Copper Complexesmentioning

confidence: 98%

“…Such an increase in regioselectivity can be explained by the fact that oxidation in the case of complex 18 occurs in the cavities formed by bulky ligands surrounding the reaction centers of the catalyst molecule. As in the case of iron ions, a large number of works have been devoted to silsesquioxane complexes with copper and their use in catalytic oxidation [73][74][75][76][77][78][79][80][81][82][83][84][85][86][87][88]. A few structures of the catalysts used in the most recent years are shown in Figures 12-15.…”

Section: Oxidation Catalyzed By Copper Complexesmentioning

confidence: 99%

“…Concentrations of cyclohexanol and cyclohexanone were measured both before (A)and after reduction (B) with PPh3 (used method of Shul'pin). Adapted from[81], Copyright (2018) with permission of Wiley.…”

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confidence: 99%

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Oxidation of Organic Compounds with Peroxides Catalyzed by Polynuclear Metal Compounds

Shul’pin

Shul’pina

2021

Catalysts

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The review describes articles that provide data on the synthesis and study of the properties of catalysts for the oxidation of alkanes, olefins, and alcohols. These catalysts are polynuclear complexes of iron, copper, osmium, nickel, manganese, cobalt, vanadium. Such complexes for example are: [Fe2(HPTB)(m-OH)(NO3)2](NO3)2·CH3OH·2H2O, where HPTB-¼N,N,N0,N0-tetrakis(2-benzimidazolylmethyl)-2-hydroxo-1,3-diaminopropane; complex [(PhSiO1,5)6]2[CuO]4[NaO0.5]4[dppmO2]2, where dppm-1,1-bis(diphenylphosphino)methane; (2,3-η-1,4-diphenylbut-2-en-1,4-dione)undecacarbonyl triangulotriosmium; phenylsilsesquioxane [(PhSiO1.5)10(CoO)5(NaOH)]; bi- and tri-nuclear oxidovanadium(V) complexes [{VO(OEt)(EtOH)}2(L2)] and [{VO(OMe)(H2O)}3(L3)]·2H2O (L2 = bis(2-hydroxybenzylidene)terephthalohydrazide and L3 = tris(2-hydroxybenzylidene)benzene-1,3,5-tricarbohydrazide); [Mn2L2O3][PF6]2 (L = 1,4,7-trimethyl-1,4,7-triazacyclononane). For comparison, articles are introduced describing catalysts for the oxidation of alkanes and alcohols with peroxides, which are simple metal salts or mononuclear metal complexes. In many cases, polynuclear complexes exhibit higher activity compared to mononuclear complexes and exhibit increased regioselectivity, for example, in the oxidation of linear alkanes. The review contains a description of some of the mechanisms of catalytic reactions. Additionally presented are articles comparing the rates of oxidation of solvents and substrates under oxidizing conditions for various catalyst structures, which allows researchers to conclude about the nature of the oxidizing species. This review is focused on recent works, as well as review articles and own original studies of the authors.

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Section: Oxidation Catalyzed By Copper Complexesmentioning

confidence: 91%

“…First examples of heptanuclear cage silsesquioxanes, (PhSiO1.5)14(CuO)7 18 and (Me-SiO1.5)14(CuO)7 19, were obtained [81]. It should be noted that in Ref.…”

Section: Oxidation Catalyzed By Copper Complexesmentioning

confidence: 98%

Section: Oxidation Catalyzed By Copper Complexesmentioning

confidence: 99%

mentioning

confidence: 99%

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Oxidation of Organic Compounds with Peroxides Catalyzed by Polynuclear Metal Compounds

Shul’pin

Shul’pina

2021

Catalysts

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“…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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Metal-Catalyzed Oxidation of C–H Compounds with Peroxides in Unconventional Solvents

Shul’pin

2019

Green Chemistry and Sustainable Technology

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

Cited by 27 publications

References 69 publications

Oxidation of Organic Compounds with Peroxides Catalyzed by Polynuclear Metal Compounds

Oxidation of Organic Compounds with Peroxides Catalyzed by Polynuclear Metal Compounds

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

Metal-Catalyzed Oxidation of C–H Compounds with Peroxides in Unconventional Solvents

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

Cited by 27 publications

References 69 publications

Oxidation of Organic Compounds with Peroxides Catalyzed by Polynuclear Metal Compounds

Oxidation of Organic Compounds with Peroxides Catalyzed by Polynuclear Metal Compounds

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

Metal-Catalyzed Oxidation of C–H Compounds with Peroxides in Unconventional Solvents

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