Sterically hindered tetrylenes based on new 1,10-phenanthroline-containing diols: initiators for ε-caprolactone polymerization

Mankaev, Badma N.; Zaitsev, Kirill V.; Зайцева, Г. С.; Чураков, А. В.; Egorov, Mikhail P.; Karlov, Sergey S.

doi:10.1007/s11172-019-2396-4

Cited by 11 publications

(4 citation statements)

References 25 publications

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“…Among the stannylenes studied as initiators of the polymerization of lactide, such as ε-caprolactone, as well as the copolymerization of lactide and glycolide, and lactide and trimethylene carbonate, there were derivatives containing the following structural fragments, in which the tin atom (+2) is di-, tri-, or tetracoordinated. The results of the polymerization experiments performed demonstrate the promise of using such complexes in catalysis (Figure 1) [12][13][14][15][16][17][18]. Narrow molecular weight distribution due to the absence of side reactions from transesterification remains relevant, given the fact that the scope of biodegradable polymers is their use in medicine as materials for controlled drug delivery systems, slow-release medication administration, tissue engineering scaffolds, bone tissue engineering, the formation of artificial organs, nerve regeneration and wound healing, long-term implants [19,20], and the synthesis of new initiators based on non-toxic metals, which produce PLA and PCL in a controlled manner with high molecular weights.…”

Section: Introductionmentioning

confidence: 76%

Section: Introductionmentioning

confidence: 77%

“…One-site magnesium complexes show much higher activity in ROP. So, in the scientific group of Nifant'ev, the magnesium complex BuMg(BHT)(THF) 2 14 (Figure 5) was studied, which showed extremely high activity in the ROP of ε-CL ([ε-CL]:[BuMg(BHT)(THF) 2 ] = 100:1, total monomer conversion in 1 min at 20 • C, M n = 10,100, Ð = 1.39) [18]. Later, the polymerization of this complex in ROP LA was studied, in which it also turned out to be highly active ([L-LA]:[BuMg(BHT)(THF) 2 ] = 100:1, 99% conversion, at 20 • C, M n = 12,520, Ð = 1.97).…”

Section: Anionic Ropmentioning

confidence: 99%

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Metal Complexes in the Synthesis of Biodegradable Polymers: Achievements and Prospects

Mankaev,

Karlov

2023

Materials

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This review describes recent advances in the synthesis of homopolymers of lactide and related cyclic esters via ring-opening polymerization (ROP) in the presence of metal complexes based on group 1, 2, 4, 12, 13 and 14 metals. Particular attention is paid to the influence of the initiator structure on the properties of the obtaining homo- and copolymers. Also, a separate chapter is devoted to the study of metal complexes in the synthesis of copolymers of lactide and lactones. This review highlights the efforts made over the last ten years or so, and shows how main-group metals have received increasing attention in the field of the polymerization of lactide and related cyclic esters.

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Section: Introductionmentioning

confidence: 76%

Section: Introductionmentioning

confidence: 77%

Section: Anionic Ropmentioning

confidence: 99%

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Metal Complexes in the Synthesis of Biodegradable Polymers: Achievements and Prospects

Mankaev,

Karlov

2023

Materials

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“…Until today several studies have been reported that show that stannylenes are reactive toward the polymerization of cyclic esters 36,44,45,[89][90][91][92] . Mainly stannylenes are used as catalysts and initiators of the polymerization of lactones.…”

Section: Metallylenes Reactivitymentioning

confidence: 99%

Sn, Ge and Al compounds stabilized by bis-amidine, bis-sulfonimidamide, and Schiff base ligands: synthesis and reactivity

Riveros¹

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Teniendo en cuenta los problemas actuales relacionados con el medio ambientales que afectan a nuestro planeta, como el efecto invernadero, el calentamiento global y la acumulación de residuos plásticos, producidos por la emisión de gases como CO2 a la atmosfera y el uso indiscriminado de plásticos, es necesario estrategias para disminuir estos problemas, y una de estas es desarrollar sistemas catalíticos mediante la síntesis de nuevos compuestos, para así usar los contaminantes como CO2, CO, CH4, etc. para obtener nuevos compuestos con valor agregado. Por lo tanto, en este proyecto de tesis se sintetizaron germilenos y estanilenos con ligandos bisamidinas con un puente rígido de naftaleno. Estos sistemas fueron usados como catalizadores en reacciones de polimerización de esteres cíclicos, pero no presentaron la reactividad deseada. Sin embargo, para entender y saber las propiedades de estos nuevos compuestos y la reactividad que poseen es que de igual manera se probaron frente a reacciones del tipo oxidación, adición oxidativa, coordinación y transmetalación. Por otra parte, fue posible sintetizar nuevos complejos bis-aluminio con ligando bis-amidinas con un puente rígido de naftaleno, los cuales fueron testeado como catalizador para la obtención de carbonatos cíclicos a partir de epóxidos y CO2, que presentaron de moderada a excelente conversión. Asimismo, fue posible obtener un complejo de aluminio usando el mismo ligando bis-amidina, pero incorporando yoduros en su estructura para utilizarlo como un catalizador de un componente, pero desafortunadamente no presento actividad catalítica. Se sintetizo un ligando base de Schiff derivado de ferroceno, con su respectivo complejo de aluminio, el cual presentó baja actividad catalítica para la obtención de carbonatos cíclicos a partir de epóxidos y CO2. En cuanto a los ligandos bis-sulfonimidamida que contengan un puente en su estructura, a pesar de las múltiples pruebas, no fue posible obtenerlos.

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Synthesis of ONO‐Ligated Tetrylenes Based on 2,6‐bis(2‐Hydroxyphenyl)pyridines: Influence of Ligand Sterics on the Structure of the Products

et al. 2023

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A series of novel tetrylenes based on three 2,6‐bis(2‐hydroxyphenyl)pyridines 4 a–4 c have been obtained by the reaction of Lappert's tetrylenes E[N(SiMe3)2]2 (E=Ge, Sn) with corresponding tridentate pyridine‐linked phenol‐based ligands. It was found that the structure of the ligand and the size of the atom of the group 14 element drastically affect the structure of the reaction product. Ligand 4 c with a bulky tert‐butyl group leads to monomeric tetrylenes, while ligands with less bulky groups lead to bis‐ligand derivatives of M(IV) (M=Ge, Sn) and a coordination polymer. Also, derivatives of germanium (IV) and tin (IV) were obtained by the metathesis reaction of MCl4 (M=Ge, Sn) with lithium phenoxides. The compositions and structures of the novel compounds were established by elemental analysis and 1H, 13C, 119Sn (5–7), 1H DOSY (6) NMR spectroscopy, in the solid state by X‐ray diffraction analysis (germylene 10, stannylene 6, Ge4+ compound 8, Sn4+ compound 7) and 119Sn Mössbauer spectrum of tin complex 6. All the synthesized tetrylenes are monomeric. Tetrylenes 6 and 10 were characterized by cyclic voltammetry. A study of the redox behavior of 6, 10 by cyclic voltammetry on a glassy carbon working electrode in acetonitrile solution of 0.1 M Bu4NPF6 as a supporting electrolyte showed that these compounds can be both oxidized and reduced electrochemically in the accessible potential range.

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Sterically hindered tetrylenes based on new 1,10-phenanthroline-containing diols: initiators for ε-caprolactone polymerization

Cited by 11 publications

References 25 publications

Metal Complexes in the Synthesis of Biodegradable Polymers: Achievements and Prospects

Metal Complexes in the Synthesis of Biodegradable Polymers: Achievements and Prospects

Sn, Ge and Al compounds stabilized by bis-amidine, bis-sulfonimidamide, and Schiff base ligands: synthesis and reactivity

Synthesis of ONO‐Ligated Tetrylenes Based on 2,6‐bis(2‐Hydroxyphenyl)pyridines: Influence of Ligand Sterics on the Structure of the Products

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