Cage-like metallasilsesquioxanes in catalysis: A review

Levitsky, Mikhail M.; Yalymov, Alexey I.; Kulakova, Alena N.; Petrov, Аrtem А.; Bilyachenko, Аlexey N.

doi:10.1016/j.molcata.2016.06.016

Cited by 67 publications

(32 citation statements)

References 41 publications

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“…Specific representatives of cage metallacomplexes, namely cagelike metallasilsesquioxanes (CLMSs), are being intensely studied as (pre)catalysts for numerous chemical processes of high relevance . Cage metallasilsesquioxanes were found to be active in alkene polymerization, epoxidation or epoxide ring opening, metathesis, hydroformylation, Ullmann–Goldberg condensation and amidation .…”

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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“…Among the huge variety of 3 D polycyclic (cage) metal‐containing complexes, those based on structural silsesquioxane (RSiO 1.5 ) fragments attract special attention as systems that simulate metal‐center‐grafting to silica surfaces perfectly in heterogeneous catalytic applications . Such compounds (cage‐like metallasilsesquioxanes, CLMSs) are also (i) active in homogeneous catalysis, (ii) demonstrate specific (spin glass) magnetic properties, or (iii) provide opportunities for unusual reactivity and structural reorganization governed by thermal treatment . The most demanded synthetic approaches to CLMSs include reactions using cubane, cyclic, and trisilanol synthons as well as self‐assembly or transmetalation procedures.…”

Section: Introductionmentioning

confidence: 99%

Ionic Complexes of Tetra‐ and Nonanuclear Cage Copper(II) Phenylsilsesquioxanes: Synthesis and High Activity in Oxidative Catalysis

et al. 2017

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Herein, we describe an approach to cage metallasilsesquioxanes by self‐assembly with 1,2‐bis(diphenylphosphino)ethane as a key reactant. This approach allowed us to achieve a unique family of complexes that includes anionic tetra‐ and nonanuclear cage copper(II) sodium silsesquioxane and cationic copper(I) 1,2‐bis(diphenylphosphino)ethane components. Additional representatives of this intriguing metallasilsesquioxane family (Cu9Na6 and Cu9Na3Cs3) were obtained through the replacement of the original ethanol‐based reaction medium by DMSO. The fascinating structural peculiarities of all products were established by using XRD and topological studies. Initial tests for the application of the synthesized complexes as catalysts revealed their very high activity in the homogeneous oxidation of alkanes and alcohols to produce alkyl hydroperoxides, ketones, and amides.

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“…Cage metallasilsesquioxanes (CLMSs) [1][2][3][4][5][6][7][8][9][10] are popular objects for the investigation of regularities in the insertion of metal ions into the siloxane matrix [11][12][13][14][15][16][17][18], the study of catalytic [19][20][21][22][23][24] properties, magnetic (spin) glass [25], as well as the study of nanoparticles [26] and macrocyclic siloxane material [27] formation.…”

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confidence: 99%

Palanquin-Like Cu4Na4 Silsesquioxane Synthesis (via Oxidation of 1,1-bis(Diphenylphosphino)methane), Structure and Catalytic Activity in Alkane or Alcohol Oxidation with Peroxides

et al. 2019

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The self-assembly synthesis of copper-sodium phenylsilsesquioxane in the presence of 1,1-bis(diphenylphosphino)methane (dppm) results in an unprecedented cage-like product: [(PhSiO 1,5 ) 6 ] 2 [CuO] 4 [NaO 0.5 ] 4 [dppmO 2 ] 2 1. The most intriguing feature of the complex 1 is the presence of two oxidized dppm species that act as additional O-ligands for sodium ions. Two cyclic phenylsiloxanolate (PhSiO 1,5 ) 6 ligands coordinate in a sandwich manner with the copper(II)-containing layer of the cage. The structure of 1 was established by X-ray diffraction analysis. Complex 1 was shown to be a very good catalyst in the oxidation of alkanes and alcohols with hydrogen peroxide or tert-butyl hydroperoxide in acetonitrile solution. Thus, cyclohexane (CyH), was transformed into cyclohexyl hydroperoxide (CyOOH), which could be easily reduced by PPh 3 to afford stable cyclohexanol with a yield of 26% (turnover number (TON) = 240) based on the starting cyclohexane. 1-Phenylethanol was oxidized by tert-butyl hydroperoxide to give acetophenone in an almost quantitative yield. The selectivity parameters of the oxidation of normal and branched alkanes led to the conclusion that the peroxides H 2 O 2 and tert-BuOOH, under the action of compound (1), decompose to generate the radicals HO • and tert-BuO • which attack the C-H bonds of the substrate.

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Cage-like metallasilsesquioxanes in catalysis: A review

Cited by 67 publications

References 41 publications

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

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

Ionic Complexes of Tetra‐ and Nonanuclear Cage Copper(II) Phenylsilsesquioxanes: Synthesis and High Activity in Oxidative Catalysis

Palanquin-Like Cu4Na4 Silsesquioxane Synthesis (via Oxidation of 1,1-bis(Diphenylphosphino)methane), Structure and Catalytic Activity in Alkane or Alcohol Oxidation with Peroxides

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Cage-like metallasilsesquioxanes in catalysis: A review

Cited by 67 publications

References 41 publications

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

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

Ionic Complexes of Tetra‐ and Nonanuclear Cage Copper(II) Phenylsilsesquioxanes: Synthesis and High Activity in Oxidative Catalysis

Palanquin-Like Cu4Na4 Silsesquioxane Synthesis (via Oxidation of 1,1-bis(Diphenylphosphino)methane), Structure and Catalytic Activity in Alkane or Alcohol Oxidation with Peroxides

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

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