The first ruthenium-silsesquioxyl complexes – synthesis, structure and mechanistic implications in silylative coupling

Żak, Patrycja; Kubicki, Maciej; Marciniec, Bogdan; Rogalski, Szymon; Pietraszuk, Cezary; Frąckowiak, Dawid

doi:10.1039/c4dt00553h

Cited by 8 publications

(5 citation statements)

References 24 publications

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“…described a ruthenium‐silsesquioxyl complex active in silylative coupling reactions (Figure 1 b). [22] Jones et al. synthesized and structurally characterized Al III[23] and Zn II[27] POSS complexes and reported on their activity in the ring‐opening polymerization of rac ‐lactide.…”

Section: Introductionmentioning

confidence: 99%

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Zinc Imine Polyhedral Oligomeric Silsesquioxane as a Quattro‐Site Catalyst for the Synthesis of Cyclic Carbonates from Epoxides and Low‐Pressure CO₂

Janeta

Lis

Szafert

2020

Chemistry A European J

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In the present research, the synthesis, spectroscopic characterization, and structural investigations of a unique ZnII complex of imine‐functionalized polyhedral oligomeric silsesquioxane (POSS) is designed, and hereby described, as a catalyst for the synthesis of cyclic carbonates from epoxides and CO2. The uncommon features of the designed catalytic system is the elimination of the need for a high pressure of CO2 and the significant shortening of reaction times commonly associated with such difficult transformations like that of styrene oxide to styrene carbonate. Our studies have shown that imine‐POSS is able to chelate metal ions like ZnII to form a unique coordination complex. The silsesquioxane core and the hindrance of the side arms (their steric effect) influence the construction process of the homoleptic Zn4@POSS‐1 complex. The compound was characterized in solution by NMR (1H, 13C, 29Si), ESI‐MS, UV/Vis spectroscopy and in the solid state by thermogravimetric/differential thermal analysis (TG‐DTA), elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), cross‐polarization magic angle spinning (CP MAS) NMR (13C, 29Si) spectroscopy, and X‐ray crystallography.

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Section: Introductionmentioning

confidence: 99%

“… Selected types of silsesquioxane complexes: a) T 7 system, b) T 8 system with a metal ion directly bonded to the silsesquioxane core, c) systems with seven inert organic substituents and a single metalated site on one outside arm of the cube [21–24] …”

Section: Introductionmentioning

confidence: 99%

Zinc Imine Polyhedral Oligomeric Silsesquioxane as a Quattro‐Site Catalyst for the Synthesis of Cyclic Carbonates from Epoxides and Low‐Pressure CO₂

Janeta

Lis

Szafert

2020

Chemistry A European J

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“…A reasonable explanation reported in literature for similar systems indicates that copper salt acts as a phosphine scavenger and thus facilitates the formation of catalytically active species. 14,15 Both reaction systems were tested using different 4-styryl substituted derivatives and in each case complete conversion of silsesquioxyl substrate 1A was achieved.…”

Section: Resultsmentioning

confidence: 99%

“…General procedure for the synthesis of functionalized E,Earylene-silsesquioxanes derivatives oligomers (9)(10)(11)(12)(13)(14)(15) By metathetic copolymerization (ADMET). A 5 mL glass reactor equipped with a reux condenser and magnetic stirring bar was charged under argon with divinylsilsesquioxane (1B) (0.1 g, 7.52 Â 10 À5 mol), diolen (7.52 Â 10 À5 mol) and dichloromethane (2 mL).…”

Section: Methodsmentioning

confidence: 99%

Synthesis and characterization of functionalized molecular and macromolecular double-decker silsesquioxane systems

et al. 2016

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“…Furthermore, a ruthenium-containing POSS was examined in silylative couplings. 21 There are also known Al 3+ and Zn 2+ POSS species active in the ROP of rac -lactide. 22 , 23 Also, it was shown that a reaction between ZnR 2 (R = OAc, Et) and fully substituted imine-POSS leads to a tetrazinc(II) compound.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Crystal Structures, and Optical and Magnetic Properties of Samarium, Terbium, and Erbium Coordination Entities Containing Mono-Substituted Imine Silsesquioxane Ligands

et al. 2023

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Mono-substituted cage-like silsesquioxanes of the T8-type can play the role of potential ligands in the coordination chemistry. In this paper, we report on imine derivatives as ligands for samarium, terbium, and erbium cations and discuss their efficient synthesis, crystal structures, and magnetic and optical properties. X-ray analysis of the lanthanide coordination entities [MCl3(POSS)3]·2THF [M = Er3+ (3), Tb3+ (4), Sm3+ (5)] showed that all three compounds crystallize in the same space group with similar lattice parameters. All compounds contain an octahedrally coordinated metal atom, and additionally, 3 and 5 structures are strictly isomorphous. However, surprisingly, there are two different molecules in the crystal structure of the terbium coordination entity 4, monomer (sof 65%) and dimer (sof 35%), with one and two metal centers. Absorption measurements of the investigated materials recorded at 300 K showed that regardless of the lanthanide involved, their energy band gap equals 2.7 eV. Moreover, the analogues containing Tb3+ and Sm3+ exhibit luminescence typical of these rare earth ions in the visible and infrared spectral range, while the compound with Er3+ does not generate any emission. Direct current variable-temperature magnetic susceptibility measurements on polycrystalline samples of 3–5 were performed between 1.8 and 300 K. The magnetic properties of 3 and 4 are dominated by the crystal field effect on the Er3+ and Tb3+ ions, respectively, hiding the magnetic influence between the magnetic cations of adjacent molecules. Complex 5 exhibits a nature typical for the paramagnetism of the samarium(III) cation.

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The first ruthenium-silsesquioxyl complexes – synthesis, structure and mechanistic implications in silylative coupling

Cited by 8 publications

References 24 publications

Zinc Imine Polyhedral Oligomeric Silsesquioxane as a Quattro‐Site Catalyst for the Synthesis of Cyclic Carbonates from Epoxides and Low‐Pressure CO₂

Zinc Imine Polyhedral Oligomeric Silsesquioxane as a Quattro‐Site Catalyst for the Synthesis of Cyclic Carbonates from Epoxides and Low‐Pressure CO₂

Synthesis and characterization of functionalized molecular and macromolecular double-decker silsesquioxane systems

Synthesis, Crystal Structures, and Optical and Magnetic Properties of Samarium, Terbium, and Erbium Coordination Entities Containing Mono-Substituted Imine Silsesquioxane Ligands

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The first ruthenium-silsesquioxyl complexes – synthesis, structure and mechanistic implications in silylative coupling

Cited by 8 publications

References 24 publications

Zinc Imine Polyhedral Oligomeric Silsesquioxane as a Quattro‐Site Catalyst for the Synthesis of Cyclic Carbonates from Epoxides and Low‐Pressure CO2

Zinc Imine Polyhedral Oligomeric Silsesquioxane as a Quattro‐Site Catalyst for the Synthesis of Cyclic Carbonates from Epoxides and Low‐Pressure CO2

Synthesis and characterization of functionalized molecular and macromolecular double-decker silsesquioxane systems

Synthesis, Crystal Structures, and Optical and Magnetic Properties of Samarium, Terbium, and Erbium Coordination Entities Containing Mono-Substituted Imine Silsesquioxane Ligands

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Zinc Imine Polyhedral Oligomeric Silsesquioxane as a Quattro‐Site Catalyst for the Synthesis of Cyclic Carbonates from Epoxides and Low‐Pressure CO₂

Zinc Imine Polyhedral Oligomeric Silsesquioxane as a Quattro‐Site Catalyst for the Synthesis of Cyclic Carbonates from Epoxides and Low‐Pressure CO₂