Amine elimination of Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 with aminophenol H[ON]{H[ON]=2-(CH2 NC5 H10)-4,6-tBu2-C6 H3OH}in 1:2 molar ratio in THF gave the monometallic rare-earth metal amide complexes[ON]2 LnN(SiMe3)2(Ln=Yb(...Amine elimination of Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 with aminophenol H[ON]{H[ON]=2-(CH2 NC5 H10)-4,6-tBu2-C6 H3OH}in 1:2 molar ratio in THF gave the monometallic rare-earth metal amide complexes[ON]2 LnN(SiMe3)2(Ln=Yb(1),Y(2),Gd(3),Sm(4),Nd(5))in 57%-73%isolated yields.All these complexes were characterized by elemental analysis.The molecular structures of complexes 1-4 were determined by single crystal X-ray diffraction.These complexes are highly active for L-Iactide polymerization to give high molecular weight polymers with unimodal molecular weight distributions.In addition,these complexes can also initiate rac-lactide polymerization with high activity to afford heterotactic-rich polylactides.展开更多
The syntheses of a library of new chiral aminophenolate bidentate O,N-type ligands HOC<sub>6</sub>H<sub>4</sub>(2-R- 4-R′)CH<sub>2</sub>N(Me)CH(Me)C<sub>6</sub>H<sub...The syntheses of a library of new chiral aminophenolate bidentate O,N-type ligands HOC<sub>6</sub>H<sub>4</sub>(2-R- 4-R′)CH<sub>2</sub>N(Me)CH(Me)C<sub>6</sub>H<sub>5</sub> [R = R′ = Bu<sup>t</sup>, 1;R = R′ = Pent, 2;R = Bu<sup>t</sup>, R′ = Me, 3;R = Me, R′ = Bu<sup>t</sup>, 4;R = R′ = Me, 5] and tridentate O,N,O-type ligands HOC<sub>6</sub>H<sub>4</sub>(2,4-Bu<sup>t</sup>)CH = NCH(R′′)C<sub>6</sub>H<sub>5</sub> [R′′ = Me, 6;R′′ = CH<sub>2</sub>OMe, 7] are reported. These ligands were characterized by elemental analysis, nuclear magnetic resonance spectroscopy (<sup>1</sup>H &<sup> 13</sup>C), and single crystal X-ray diffraction. These ligands serve as chiral auxiliaries for inorganic chemists to design chiral metal-based complexes for asymmetric catalysis and stereoselective polymerization reactions. Three new heteroleptic zinc complexes based on these ligands have been synthesized in moderate yields via a ligand-exchange transamination reaction between homoleptic [Zn(N(SiMe<sub>3</sub>)<sub>2</sub>)<sub>2</sub>] and one equivalent of corresponding ligands to afford [L<sup>3</sup>ZnN- (SiMe<sub>3</sub>)<sub>2</sub>] (3a), [L<sup>4</sup>ZnN(SiMe<sub>3</sub>)<sub>2</sub>] (4a), and [L<sup>7</sup>ZnN(SiMe<sub>3</sub>)<sub>2</sub>] (7a). Solvent-free polymerization of raclactide at 130°C using these zinc compounds yielded atactic polylactides with Mw 10,000 g/mol and narrow polydispersity of 1.3.展开更多
An aminophenol ligand, N,N,N＇-tri（2-hydroxy-5-methylbenzyl）-l,2-ethanediamine, was prepared through the Marmich reaction, and structurally characterized by NMR, IR, MS and single-crystal X-ray diffraction. The titl...An aminophenol ligand, N,N,N＇-tri（2-hydroxy-5-methylbenzyl）-l,2-ethanediamine, was prepared through the Marmich reaction, and structurally characterized by NMR, IR, MS and single-crystal X-ray diffraction. The title compound （C26H32N2O3, Mr = 420.54） belongs to the monoclinic system, space group P21/n with a = 8.6233（14）, b = 10.2655（16）, c = 26.017（4） A, β = 95.797（2）°, V = 2291.3（6） A^3, Z = 4, the final R = 0.0461 and wR = 0.1139 for 4267 unique reflections （Rint = 0.028） with 11691 observed ones （I〉 2a（I））.展开更多
Two ytterbium complexes stabilized by phenoxy（quinolinyl）amide ligand 3,5-But2-2-OC6H2CH2N-8-C9H6N （L） were synthesized and characterized. Reaction of anhydrous YbC13 with 1 equiv, of LLi2 in THF gave the ytterbiu...Two ytterbium complexes stabilized by phenoxy（quinolinyl）amide ligand 3,5-But2-2-OC6H2CH2N-8-C9H6N （L） were synthesized and characterized. Reaction of anhydrous YbC13 with 1 equiv, of LLi2 in THF gave the ytterbium chloride [LYbCI（THF）]2 （1） in 73% yield. A further reaction of complex 1 with equimolar of NaN（SiMe3）2 in THF afforded the unexpected heterobimetallic ＂ate＂-complex L2YbNa（THF）2 （2） via a ligand redistribution reaction. Complex 2 could also be prepared in high isolated yield by the reaction of anhydrous YbC13 with 2 equiv, of LNa2 generated in situ. Both complexes 1 and 2 were characterized by IR spectroscopy, elemental analysis, and sin- gle-crystal X-ray diffraction analysis. It was found that complex 2 was an effective catalyst for the addition reaction of aromatic amines to carbodiimides.展开更多
The exploration of C2-symmetric chiral aminophenols and aminonaphthols is described. Seven new ligands have been successfully synthesized using Mannich reaction as a key step. Four of them have C2-symmetry and their s...The exploration of C2-symmetric chiral aminophenols and aminonaphthols is described. Seven new ligands have been successfully synthesized using Mannich reaction as a key step. Four of them have C2-symmetry and their structure has been fully characterized by means of NMR and X-ray crystallography.展开更多
The oxidative polycondensation reaction conditions of 2-[(2-hydroxyphenyliminomethylbenzylidene)amino- phenol](2-HPIMBAP)has been accomplished by using air O_2 and NaOCl oxidants in an aqueous alkaline medium between ...The oxidative polycondensation reaction conditions of 2-[(2-hydroxyphenyliminomethylbenzylidene)amino- phenol](2-HPIMBAP)has been accomplished by using air O_2 and NaOCl oxidants in an aqueous alkaline medium between 50-90℃.The optimum reaction conditions of the oxidative polycondensation and the main parameters of the process were established.At the optimum reaction conditions,yield of the products were found to be 67.72% and 61.49% for air O_2 and NaOCl oxidants respectively.The structures of the monomer ...展开更多
The optimum reaction conditions of the oxidative polycondensation of 2-(thien-2-yl-methylene)aminophenol (2-TMAP) has been accomplished by using air O_2,H_2O_2 and NaOCl oxidants in an aqueous alkaline medium between...The optimum reaction conditions of the oxidative polycondensation of 2-(thien-2-yl-methylene)aminophenol (2-TMAP) has been accomplished by using air O_2,H_2O_2 and NaOCl oxidants in an aqueous alkaline medium between 20℃and 90℃.The structures of the monomer and oligomer were confirmed by FT-IR,UV-Vis,~1H-NMR and ^(13)C-NMR and elemental analysis.TGA-DTA,size exclusion chromatography(SEC) techniques and solubility tests were applied for characterization.The ~1H-NMR and ^(13)C-NMR data show that the polymeriz...展开更多
Diphenoxo bridged dinuclear zinc complexes[Zn_(2)(OMe-Phimp)_(2)(Cl)_(2)](1)(OMe-PhimpH=(E)-4-methoxy-2-((2-phenyl-2-(pyridin-2-yl)hydrazono)methyl)phenol),[Zn_(2)(Me-Phimp)_(2)(Cl)_(2)](2)(Me-PhimpH=(E)-4-methyl-2-((...Diphenoxo bridged dinuclear zinc complexes[Zn_(2)(OMe-Phimp)_(2)(Cl)_(2)](1)(OMe-PhimpH=(E)-4-methoxy-2-((2-phenyl-2-(pyridin-2-yl)hydrazono)methyl)phenol),[Zn_(2)(Me-Phimp)_(2)(Cl)_(2)](2)(Me-PhimpH=(E)-4-methyl-2-((2-phenyl-2-(pyridin-2-yl)hydrazono)methyl)phenol),[Zn_(2)(N-Phimp)_(2)(Cl)_(2)]·CH_(3)CN(3·CH_(3)CN)(N-PhimpH=(E)-1-((2-phenyl-2-(pyridin-2-yl)hydrazono)methyl)naphthalen-2-ol)and[Zn_(2)(Phimp)_(2)(Cl)_(2)](4)(PhimpH=(E)-2-((2-phenyl-2-(pyridin-2-yl)hydrazono)methyl)phenol)were synthesized and spectroscopically characterized.The molecular structures of 1 and 3·CH_(3)CN were determined using X-ray crystallography.DFT and TD-DFT calculations were performed to optimize the molecular geometry,interpret the spectroscopic results and investigate the contribution of the ligands to the redox properties of the complexes.Phenoxyl radical complexes were generated in solution via chemical oxidation using ceric ammonium nitrate(CAN)and the redox properties were examined through cyclic voltammetric measurements.All the dinuclear zinc complexes were found to be highly active in catalyzing the oxidation of the primary alcohols 3,5-di-tert-butylcatechol and o-aminophenol.The catalytic activity was found to be in the order of complex 1>complex 2>complex 4>complex 3 for both calechol oxidation and o-aminophenol oxidation.An EPR experiment clearly hinted at the generation of a radical during the oxidation of catechol and o-aminophenol.Reaction models for these processes were proposed and theoretical studies were performed to support the proposed mechanism.ESI-MS spectra clearly indicate the formation of a catalyst–substrate adduct by removal of one Cl−ion.展开更多
The low-temperature fabrication of hard carbon is of significant importance for the development of lithium-ion batteries towards grid-scale energy storage.Despite their high capacity and coulombic efficiency,conventio...The low-temperature fabrication of hard carbon is of significant importance for the development of lithium-ion batteries towards grid-scale energy storage.Despite their high capacity and coulombic efficiency,conventional methods suffer from high pyrolysis temperatures and/or complex procedures,resulting in high costs.Herein,we innovatively proposed a catalytic microdomain engineering strategy,where 3-aminophenol was initially coordinated with Fe^(3+)ions and then polymerized to formaldehyde,forming a catalytic microdomain composed of[Fe(3-AP)_(x)]^(3+)units within the resin precursor.Material characterization suggests the uniform chemical composition of the resin precursor,and in situ DRIFT spectra revealed that the resin precursor features a low N-C-O rearrangement temperature,enabling low-temperature fabrication of high-performance hard carbon.Experimentally,FeOC-400 delivered a high reversible capacity of 566 mAh g^(-1) after 250 cycles at 0.1 A g^(-1) and a capacity retention of 95.6%after 5000 cycles at 10.0 A g^(-1),endowing the FeOC-400||LFP full cell with a high energy density of over 175.7 Wh kg^(-1)(based on the total mass of FeOC-400 and LFP).The findings of this study can provide new insight into the design of high-capacity and fast-charging hard carbon,and the catalytic microdomain engineering strategy is applicable to the low-cost fabrication of hard carbon towards grid-scale energy devices.展开更多
We report the use of palladium nanoparticles(Pd NPs)immobilized on m-aminophenol/formaldehyde resin(APF)-derived porous carbon spheres(Pd@PCS)as heterogeneous catalysts for the reduction of organic dyes.The morphology...We report the use of palladium nanoparticles(Pd NPs)immobilized on m-aminophenol/formaldehyde resin(APF)-derived porous carbon spheres(Pd@PCS)as heterogeneous catalysts for the reduction of organic dyes.The morphology,structure,surface compositions,and textural properties of PCS and the Pd@PCS catalyst were characterized fully to document the excellent catalytic efficiency of Pd@PCS composites.Pd NPs of mean particle size ca.12±0.8 nm were highly dispersed on the surface of PCSs.展开更多
Three 2-{(3R,7aS)-1,1-disubstituted-tetrahydro-1H-pyrrolo[1,2-c][1,3]oxazol-3-yl}phenols have been synthesized from salicylaldehyde and amino alcohols derived from L-proline,and used as ligands hi enantioselective add...Three 2-{(3R,7aS)-1,1-disubstituted-tetrahydro-1H-pyrrolo[1,2-c][1,3]oxazol-3-yl}phenols have been synthesized from salicylaldehyde and amino alcohols derived from L-proline,and used as ligands hi enantioselective addition of diethylzinc to aldehydes,the ee values of obtained secondary alcohols were found in the range of 0-90%.展开更多
基金Project supported by the National Natural Science Foundation of China(21572205,21971130,21871198,21674070)the Natural Science Foundation of Zhejiang Province(LY19B040002)+2 种基金the State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciencesthe Natural Science Foundation of Ningbo Municipal(2019A610030,2019A610129)K.C.Wong Magna Fund in Ningbo University。
文摘Amine elimination of Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 with aminophenol H[ON]{H[ON]=2-(CH2 NC5 H10)-4,6-tBu2-C6 H3OH}in 1:2 molar ratio in THF gave the monometallic rare-earth metal amide complexes[ON]2 LnN(SiMe3)2(Ln=Yb(1),Y(2),Gd(3),Sm(4),Nd(5))in 57%-73%isolated yields.All these complexes were characterized by elemental analysis.The molecular structures of complexes 1-4 were determined by single crystal X-ray diffraction.These complexes are highly active for L-Iactide polymerization to give high molecular weight polymers with unimodal molecular weight distributions.In addition,these complexes can also initiate rac-lactide polymerization with high activity to afford heterotactic-rich polylactides.
文摘The syntheses of a library of new chiral aminophenolate bidentate O,N-type ligands HOC<sub>6</sub>H<sub>4</sub>(2-R- 4-R′)CH<sub>2</sub>N(Me)CH(Me)C<sub>6</sub>H<sub>5</sub> [R = R′ = Bu<sup>t</sup>, 1;R = R′ = Pent, 2;R = Bu<sup>t</sup>, R′ = Me, 3;R = Me, R′ = Bu<sup>t</sup>, 4;R = R′ = Me, 5] and tridentate O,N,O-type ligands HOC<sub>6</sub>H<sub>4</sub>(2,4-Bu<sup>t</sup>)CH = NCH(R′′)C<sub>6</sub>H<sub>5</sub> [R′′ = Me, 6;R′′ = CH<sub>2</sub>OMe, 7] are reported. These ligands were characterized by elemental analysis, nuclear magnetic resonance spectroscopy (<sup>1</sup>H &<sup> 13</sup>C), and single crystal X-ray diffraction. These ligands serve as chiral auxiliaries for inorganic chemists to design chiral metal-based complexes for asymmetric catalysis and stereoselective polymerization reactions. Three new heteroleptic zinc complexes based on these ligands have been synthesized in moderate yields via a ligand-exchange transamination reaction between homoleptic [Zn(N(SiMe<sub>3</sub>)<sub>2</sub>)<sub>2</sub>] and one equivalent of corresponding ligands to afford [L<sup>3</sup>ZnN- (SiMe<sub>3</sub>)<sub>2</sub>] (3a), [L<sup>4</sup>ZnN(SiMe<sub>3</sub>)<sub>2</sub>] (4a), and [L<sup>7</sup>ZnN(SiMe<sub>3</sub>)<sub>2</sub>] (7a). Solvent-free polymerization of raclactide at 130°C using these zinc compounds yielded atactic polylactides with Mw 10,000 g/mol and narrow polydispersity of 1.3.
基金supported by Shandong Province Higher Educational Science and Technology Program (J09LB03)
文摘An aminophenol ligand, N,N,N＇-tri（2-hydroxy-5-methylbenzyl）-l,2-ethanediamine, was prepared through the Marmich reaction, and structurally characterized by NMR, IR, MS and single-crystal X-ray diffraction. The title compound （C26H32N2O3, Mr = 420.54） belongs to the monoclinic system, space group P21/n with a = 8.6233（14）, b = 10.2655（16）, c = 26.017（4） A, β = 95.797（2）°, V = 2291.3（6） A^3, Z = 4, the final R = 0.0461 and wR = 0.1139 for 4267 unique reflections （Rint = 0.028） with 11691 observed ones （I〉 2a（I））.
基金Project supported by National Natural Science Foundation of China (21072146, 21132002)the Priority Academic Program Development of Jiangsu Higher Education Institutions and Key Laboratory of Organic Synthesis of Jiangsu,Soochow University(KJS1008)for financial support
文摘Two ytterbium complexes stabilized by phenoxy（quinolinyl）amide ligand 3,5-But2-2-OC6H2CH2N-8-C9H6N （L） were synthesized and characterized. Reaction of anhydrous YbC13 with 1 equiv, of LLi2 in THF gave the ytterbium chloride [LYbCI（THF）]2 （1） in 73% yield. A further reaction of complex 1 with equimolar of NaN（SiMe3）2 in THF afforded the unexpected heterobimetallic ＂ate＂-complex L2YbNa（THF）2 （2） via a ligand redistribution reaction. Complex 2 could also be prepared in high isolated yield by the reaction of anhydrous YbC13 with 2 equiv, of LNa2 generated in situ. Both complexes 1 and 2 were characterized by IR spectroscopy, elemental analysis, and sin- gle-crystal X-ray diffraction analysis. It was found that complex 2 was an effective catalyst for the addition reaction of aromatic amines to carbodiimides.
基金This work was financially supported by the National Natural Science Foundation of China(Grant No.20172008),which is greatly appreciated.
文摘The exploration of C2-symmetric chiral aminophenols and aminonaphthols is described. Seven new ligands have been successfully synthesized using Mannich reaction as a key step. Four of them have C2-symmetry and their structure has been fully characterized by means of NMR and X-ray crystallography.
基金This work was supported by the Canakkale Onsekiz Mart University Scientific Research Projects Commission for financial support(No.2007/20).
文摘The oxidative polycondensation reaction conditions of 2-[(2-hydroxyphenyliminomethylbenzylidene)amino- phenol](2-HPIMBAP)has been accomplished by using air O_2 and NaOCl oxidants in an aqueous alkaline medium between 50-90℃.The optimum reaction conditions of the oxidative polycondensation and the main parameters of the process were established.At the optimum reaction conditions,yield of the products were found to be 67.72% and 61.49% for air O_2 and NaOCl oxidants respectively.The structures of the monomer ...
基金supported by the Government Planning Organization(GPO2002K120170-7)TUBITAK GrantsCommission for a research grant(No.TBAG-105T428).
文摘The optimum reaction conditions of the oxidative polycondensation of 2-(thien-2-yl-methylene)aminophenol (2-TMAP) has been accomplished by using air O_2,H_2O_2 and NaOCl oxidants in an aqueous alkaline medium between 20℃and 90℃.The structures of the monomer and oligomer were confirmed by FT-IR,UV-Vis,~1H-NMR and ^(13)C-NMR and elemental analysis.TGA-DTA,size exclusion chromatography(SEC) techniques and solubility tests were applied for characterization.The ~1H-NMR and ^(13)C-NMR data show that the polymeriz...
基金SERB-DST(SR/S1/IC-47/2012 dated Oct 2013),New Delhi,India for financial assistanceUGC for financial assistance。
文摘Diphenoxo bridged dinuclear zinc complexes[Zn_(2)(OMe-Phimp)_(2)(Cl)_(2)](1)(OMe-PhimpH=(E)-4-methoxy-2-((2-phenyl-2-(pyridin-2-yl)hydrazono)methyl)phenol),[Zn_(2)(Me-Phimp)_(2)(Cl)_(2)](2)(Me-PhimpH=(E)-4-methyl-2-((2-phenyl-2-(pyridin-2-yl)hydrazono)methyl)phenol),[Zn_(2)(N-Phimp)_(2)(Cl)_(2)]·CH_(3)CN(3·CH_(3)CN)(N-PhimpH=(E)-1-((2-phenyl-2-(pyridin-2-yl)hydrazono)methyl)naphthalen-2-ol)and[Zn_(2)(Phimp)_(2)(Cl)_(2)](4)(PhimpH=(E)-2-((2-phenyl-2-(pyridin-2-yl)hydrazono)methyl)phenol)were synthesized and spectroscopically characterized.The molecular structures of 1 and 3·CH_(3)CN were determined using X-ray crystallography.DFT and TD-DFT calculations were performed to optimize the molecular geometry,interpret the spectroscopic results and investigate the contribution of the ligands to the redox properties of the complexes.Phenoxyl radical complexes were generated in solution via chemical oxidation using ceric ammonium nitrate(CAN)and the redox properties were examined through cyclic voltammetric measurements.All the dinuclear zinc complexes were found to be highly active in catalyzing the oxidation of the primary alcohols 3,5-di-tert-butylcatechol and o-aminophenol.The catalytic activity was found to be in the order of complex 1>complex 2>complex 4>complex 3 for both calechol oxidation and o-aminophenol oxidation.An EPR experiment clearly hinted at the generation of a radical during the oxidation of catechol and o-aminophenol.Reaction models for these processes were proposed and theoretical studies were performed to support the proposed mechanism.ESI-MS spectra clearly indicate the formation of a catalyst–substrate adduct by removal of one Cl−ion.
基金the financial support of the Natural Science Research Project of Anhui Educational Committee(2023AH050189)the Doctoral Scientific Research Startup Foundation of Anhui Jianzhu University(Grant No.2022QDZ01)+2 种基金the Open Project Program of Key Laboratory of Functional Molecular Solids of Ministry of Education(FMS2023004)Anhui Province International Research Center on Advanced Building Materials(Grant No.JZCL2303ZR)Anhui Institute of Strategic Study on Carbon Dioxide Emissions Peak and Carbon Neutrality in Urban-Rural Development(Grant No.STY-2023-05).
文摘The low-temperature fabrication of hard carbon is of significant importance for the development of lithium-ion batteries towards grid-scale energy storage.Despite their high capacity and coulombic efficiency,conventional methods suffer from high pyrolysis temperatures and/or complex procedures,resulting in high costs.Herein,we innovatively proposed a catalytic microdomain engineering strategy,where 3-aminophenol was initially coordinated with Fe^(3+)ions and then polymerized to formaldehyde,forming a catalytic microdomain composed of[Fe(3-AP)_(x)]^(3+)units within the resin precursor.Material characterization suggests the uniform chemical composition of the resin precursor,and in situ DRIFT spectra revealed that the resin precursor features a low N-C-O rearrangement temperature,enabling low-temperature fabrication of high-performance hard carbon.Experimentally,FeOC-400 delivered a high reversible capacity of 566 mAh g^(-1) after 250 cycles at 0.1 A g^(-1) and a capacity retention of 95.6%after 5000 cycles at 10.0 A g^(-1),endowing the FeOC-400||LFP full cell with a high energy density of over 175.7 Wh kg^(-1)(based on the total mass of FeOC-400 and LFP).The findings of this study can provide new insight into the design of high-capacity and fast-charging hard carbon,and the catalytic microdomain engineering strategy is applicable to the low-cost fabrication of hard carbon towards grid-scale energy devices.
基金supported by the Ministry of Science and Technology,Taiwan(NSC 102-2113-M-002-009-MY3 to KCL)IPM gratefully acknowledges the Department of Science and Technology(DST)in India for support with the INSPIRE Faculty Award(DST/INSPIRE/04/2016/002275).
文摘We report the use of palladium nanoparticles(Pd NPs)immobilized on m-aminophenol/formaldehyde resin(APF)-derived porous carbon spheres(Pd@PCS)as heterogeneous catalysts for the reduction of organic dyes.The morphology,structure,surface compositions,and textural properties of PCS and the Pd@PCS catalyst were characterized fully to document the excellent catalytic efficiency of Pd@PCS composites.Pd NPs of mean particle size ca.12±0.8 nm were highly dispersed on the surface of PCSs.
基金Project supported by the Key Laboratory of Organic Syntheses,Jiangsu Province(No.T2109102).
文摘Three 2-{(3R,7aS)-1,1-disubstituted-tetrahydro-1H-pyrrolo[1,2-c][1,3]oxazol-3-yl}phenols have been synthesized from salicylaldehyde and amino alcohols derived from L-proline,and used as ligands hi enantioselective addition of diethylzinc to aldehydes,the ee values of obtained secondary alcohols were found in the range of 0-90%.
