A cobalt pincer complex bearing both P and C-stereogenic centers has been designed and synthesized,allowing for the development of the first cobalt-catalyzed asymmetric hydrogenation of quinoxalines under relatively m...A cobalt pincer complex bearing both P and C-stereogenic centers has been designed and synthesized,allowing for the development of the first cobalt-catalyzed asymmetric hydrogenation of quinoxalines under relatively mild conditions.Valuable chiral 1,2,3,4-tetrahydroquinoxalines could be obtained with high yields and excellent enantioselectivities(35 examples,up to>99%ee).展开更多
A nonsymmetrical PNN pincer ligand[6-(^(t)Bu_(2)PNH)C_(5)H_(4)N-2-(3-Mes)C_(3)H_(2)N_(2)]and its corresponding cobalt-N_(2)complex were synthesized and characterized.By the stoichiometric reaction of the PNN ligand li...A nonsymmetrical PNN pincer ligand[6-(^(t)Bu_(2)PNH)C_(5)H_(4)N-2-(3-Mes)C_(3)H_(2)N_(2)]and its corresponding cobalt-N_(2)complex were synthesized and characterized.By the stoichiometric reaction of the PNN ligand lithium salt with CoCl_(2),the complex 3,(PNN)CoCl,was obtained.Then,reduction of 3 with NaBHEt3under a dinitrogen atmosphere yielded complex 5,(PNN)Co(Ⅰ)(η^(1)-N_(2)).Single-crystal X-ray analysis,IR spectrum,and DFT calculations revealed that the dinitrogen in 5 was only weakly reduced by the cobalt center.The reactions of 5 with carbon monoxide and 2,6-dimethylphenyl isocyanide gave carbonyl and isocyanide complexes 6 and 7 with the release of N_(2),respectively.Furthermore,these cobalt complexes,especially complex 5,demonstrated the capacity to convert dinitrogen to N(TMS)_(3)with moderate efficiency.展开更多
A convenient colorimetric approach for visual detection of melamine in raw milk was realized by using gold nanoparticles(AuNPs)stabilized by an unsymmetrical terpyridyl zinc complex with a thymine fragment at one term...A convenient colorimetric approach for visual detection of melamine in raw milk was realized by using gold nanoparticles(AuNPs)stabilized by an unsymmetrical terpyridyl zinc complex with a thymine fragment at one terminal and a quaternary ammonium salt at the other.Even without pre-addition of melamine or relative additives,obvious color change from red to blue was observed by naked eye in the presence of trace amount of melamine,which was attributed to the alternation of aggregation state of AuNPs caused by the selective binding between the thymine fragment and melamine via triple hydrogenbonding interactions.Remarkably,the detection limit for melamine was as low as 2.4 ppb,providing a highly sensitive and efficient approach for the visual detection of melamine.展开更多
The asymmetric carbenoid C–H insertion of 3-diazooxindoles into 1,4-cyclohexadiene has been accomplished in the presence of chiral bis(imidazoline) NCN pincer iridium(Ⅲ) complexes as the catalysts. With a catalyst l...The asymmetric carbenoid C–H insertion of 3-diazooxindoles into 1,4-cyclohexadiene has been accomplished in the presence of chiral bis(imidazoline) NCN pincer iridium(Ⅲ) complexes as the catalysts. With a catalyst loading of 0.5 mol%, the reactions proceeded smoothly at 0℃ to afford a variety of chiral 3-substituted oxindoles in good yields with moderate to excellent enantioselectivities(up to 99% ee). The protocol exhibits good functional group tolerance with respect to 3-diazooxindoles and is readily scaled up to 2 mmol scale without any loss in activity and enantioselectivity. Density functional theory(DFT)calculations have been performed to better understand the reaction mechanism and to explain the stereochemical outcome of the reactions.展开更多
Comprehensive Summary Terpyridine ligands have been applied as a class of unique ligands due to their rich coordination chemistry in the catalysis.Herein,we developed a new class of C_(2)-symmetric chiral terpyridine-...Comprehensive Summary Terpyridine ligands have been applied as a class of unique ligands due to their rich coordination chemistry in the catalysis.Herein,we developed a new class of C_(2)-symmetric chiral terpyridine-pyrroloimidazolone ligands(TPy-BPI).Their catalytic activity was evaluated in the asymmetric Friedel-Crafts alkylation of indoles with 2,3-dioxopyrrolidines.Excellent yields(up to 92%)and high enantioselectivities(up to 97%ee)are obtained for a wide range of substrates under mild conditions.展开更多
The aryldiimine NCN-pincer stabilized neodymium dichloride combined with aluminum alkyls established a new type of homogeneous binary neutral Ziegler-Natta catalyst system.This system exhibited high activity and high ...The aryldiimine NCN-pincer stabilized neodymium dichloride combined with aluminum alkyls established a new type of homogeneous binary neutral Ziegler-Natta catalyst system.This system exhibited high activity and high cis-1,4 selectivity for the polymerization of isoprene (Tp=20 °C,98.2%;Tp=-20 °C,】 99%).Such catalytic performances remained under a broad range of polymerization temperatures and monomer-to-neodymium ratios (from 500 to 8000),reaching high number-average molecular weight (Mn=1582 kg/mol) and relatively narrow molecular weight distribution (PDI=1.68),which was,however,influenced by the amount and bulkiness of aluminum alkyls.Dynamic investigation of the polymerization was performed,which showed the number-average molecular weight of the resultant polyisoprene had an almost linear correlation with the conversion,suggesting,in some degree,the polymerization with this catalytic system was controllable.展开更多
A new type of dianionic Ir(Ⅲ) CCC pincer complexes(SNHC-Ir, 1a–1c) is successfully designed and synthesized by developing a one-step methodology, which involves an initial coordination of Ir(I) with the NHC and subs...A new type of dianionic Ir(Ⅲ) CCC pincer complexes(SNHC-Ir, 1a–1c) is successfully designed and synthesized by developing a one-step methodology, which involves an initial coordination of Ir(I) with the NHC and subsequent metallation of double sp2C–H bonds. This method is considerably useful over those reported by using strong coordination ligand or carbonic anion exchange,and would provide an alternative efficient template of organometallics synthesis. Experimental and density functional theory(DFT) calculation results indicate that the spirocyclic framework is a favourable factor for the facile formation and stabilization of these complexes. Primary investigation shows that chloride 1b can well catalyze homo and hetero addition of styrene derivatives and remote olefin isomerization, which represents the first catalytic application of the dianionic CCC pincer complexes.展开更多
Extracting hydrogen from methanol is a safe and cost-efficient strategy for fuel supply. This process was realized recently at a mild condition with excellent efficiency by ruthenium pincer catalysts. Despite the expe...Extracting hydrogen from methanol is a safe and cost-efficient strategy for fuel supply. This process was realized recently at a mild condition with excellent efficiency by ruthenium pincer catalysts. Despite the experimental success, the associated mechanism remains under debate. With the aid of density functional theory(DFT) calculations, an updated and self-consistent mechanism which involves Me OH-catalysed dehydrogenation of ruthenium hydride intermediate and pre-protonation of the pincer ligand was present herein. This mechanism is kinetically favoured over the previously-proposed water- or formic- acid-participated ones and more consistent with the optimal experimental condition where strong base and neat methanol solvent are used.展开更多
The asymmetric reduction of carbonyl compounds by means of the Ru-chiral diphosphine-chiral diamine catalysts is widely useful in organic synthesis where high levels of enantioselectivities have been attributed to mul...The asymmetric reduction of carbonyl compounds by means of the Ru-chiral diphosphine-chiral diamine catalysts is widely useful in organic synthesis where high levels of enantioselectivities have been attributed to multiple ligand chiral elements as well as essential stereochemical matching synergies within them.Described here is the design and discovery of new pincer-type Ru-catalysts that feature only single stereogenic element within ligands,yet the such significantly simplified structure is demonstrated to be well competent for effecting asymmetric reductions as well as kinetic resolutions over a broad range of highly functionalized ketones/alcohols,including heteroaryl substituted substrates that were challenging by known catalyst systems.Alcohols were furnished not only in excellent enantioselectivities,but with turnover numbers(up to 100,000 TONs)that reach the highest levels known to date in asymmetric transfer hydrogenation of ketones.This work should help shed light on the intricate origin of enantioselection in these important processes,and further stimulate rational understanding as well as optimization of chiral catalysts towards efficiency and simplicity.展开更多
The mineral phases and structure of pincer for the freshwater lobster were analyzed and observed by using X-ray diffraction and field-emission scanning electronic microscope with energy dispersive spectroscopy, and th...The mineral phases and structure of pincer for the freshwater lobster were analyzed and observed by using X-ray diffraction and field-emission scanning electronic microscope with energy dispersive spectroscopy, and the mechanical properties of pincer were determined by using nano-indenter and micro-tribometer. The results showed that the pincers contained Ca, Mg, C, O, Na, etc. elements and there were many amorphous mineral phases in the lobster pincers. There were many concave hollows and convex domes with seta on the surface of pincer, and some spines were observed on the surface of seta, which exhibited non-smooth surface. The exoskeleton of pincer consisted of epicuticle, exocuticle and endocuticle, and the microstructure of exocuticle and endocuticle displayed the twisted plywood structure with chitin protein fibers. The mean hardness and elastic modulus on the surface of fresh pincers were 0.27 GPa and 5.28 GPa, respectively. With the increase in distance from the surface, the hardness and elastic modulus all decreased gradually. This indicated that the transition of hardness and elastic modulus occurred from exocuticle to endocuticle. When the heat treatment temperature was lower than 200°C, the values of hardness and elastic modulus fluctuated slightly, while they increased at the temperature beyond 200°C. As the pincers slid against Si3N4 balls in water and air, the friction coefficients in water were higher than those in air. The research could provide a bio-inspired basis for the structural design of composite materials and anti-friction surface.展开更多
Considering the importance of the valorization of CO_(2),a number of phosphine-containing ruthenium pincer complexes have been successfully heterogenized using a“direct knitting”strategy without any premodification....Considering the importance of the valorization of CO_(2),a number of phosphine-containing ruthenium pincer complexes have been successfully heterogenized using a“direct knitting”strategy without any premodification.The resulting porous organometallic polymers(POMPs)with high specific-surface areas,hierarchical pores,and uniformly dispersed Ru single-sites exhibited outstanding catalytic activity toward the N-formylation of diverse amines with CO_(2).Besides excellent turnover number(TON,5×10^(5))and turnover frequency(TOF,5592 h-1),the obtained formamides were readily hydrogenated to methanol with the same catalyst.Consequently,an amine-assisted direct hydrogenation system of CO_(2)to methanol was established by POMPs with higher activity and TON(1.46×10^(4))than their molecular precursors,shedding light on the direct valorization of CO_(2)and carbon neutral recycling.展开更多
The reactions of a variety of 4,6-dimethyl-1,3-bis(imino)benzenes 2a-g derived from 4,6-dimethylisophthalaldehyde and anilines or benzylamine with palladium(II)acetate in anhydrous acetic acid under nitrogen were inve...The reactions of a variety of 4,6-dimethyl-1,3-bis(imino)benzenes 2a-g derived from 4,6-dimethylisophthalaldehyde and anilines or benzylamine with palladium(II)acetate in anhydrous acetic acid under nitrogen were investigated.Experiment results demonstrate that cyclopalladations in such condition are applicable not only to the present system under study but also to the 5-substituted bis(imino)benzenes 6,7.The molecular structure of 3b was further confirmed by X-Ray single-crystal diffraction.3b Crystallizes in orthorhombic,space group P2(1)2(1)2(1)with a=0.734 53(8),b=1.683 8(3),c=1.691 7(2)nm,α=β=γ=90°.Treatment of 2b with K2PtCl4in anhydrous acetic acid affords the corresponding NCN-platinum pincer.Carbon-carbon cross coupling reactions catalyzed with 3b were investigated.These palladium complexes have been proved to be high effective catalysts for Suzuki coupling reaction.展开更多
基金the financial support of the National Natural Science Foundation of China(No.21672133)the Opening Foundation of Key Laboratory of Applied Surface and Colloid Chemistry,Ministry of Education(No.GK202205011)the Fundamental Research Funds for the Central Universities(Nos.GK202307007 and GK202002003)。
文摘A cobalt pincer complex bearing both P and C-stereogenic centers has been designed and synthesized,allowing for the development of the first cobalt-catalyzed asymmetric hydrogenation of quinoxalines under relatively mild conditions.Valuable chiral 1,2,3,4-tetrahydroquinoxalines could be obtained with high yields and excellent enantioselectivities(35 examples,up to>99%ee).
基金supported by the National Natural Science Foundation of China(Nos.21988101 and 22201013)Beijing Natural Science Foundation(No.2222008)supported by the High-performance Computing Platform of Peking University。
文摘A nonsymmetrical PNN pincer ligand[6-(^(t)Bu_(2)PNH)C_(5)H_(4)N-2-(3-Mes)C_(3)H_(2)N_(2)]and its corresponding cobalt-N_(2)complex were synthesized and characterized.By the stoichiometric reaction of the PNN ligand lithium salt with CoCl_(2),the complex 3,(PNN)CoCl,was obtained.Then,reduction of 3 with NaBHEt3under a dinitrogen atmosphere yielded complex 5,(PNN)Co(Ⅰ)(η^(1)-N_(2)).Single-crystal X-ray analysis,IR spectrum,and DFT calculations revealed that the dinitrogen in 5 was only weakly reduced by the cobalt center.The reactions of 5 with carbon monoxide and 2,6-dimethylphenyl isocyanide gave carbonyl and isocyanide complexes 6 and 7 with the release of N_(2),respectively.Furthermore,these cobalt complexes,especially complex 5,demonstrated the capacity to convert dinitrogen to N(TMS)_(3)with moderate efficiency.
基金Financial support from the State General Administration of the People’s Republic of China for Quality Supervision and Inspection and Quarantine(No.2016QK122)the Science and Technology Projects of Jiangxi Province(No.20181BBH80007)+1 种基金Shanghai Institute of Quality Inspection and Technical Researchthe Department of Chemistry,Fudan University。
文摘A convenient colorimetric approach for visual detection of melamine in raw milk was realized by using gold nanoparticles(AuNPs)stabilized by an unsymmetrical terpyridyl zinc complex with a thymine fragment at one terminal and a quaternary ammonium salt at the other.Even without pre-addition of melamine or relative additives,obvious color change from red to blue was observed by naked eye in the presence of trace amount of melamine,which was attributed to the alternation of aggregation state of AuNPs caused by the selective binding between the thymine fragment and melamine via triple hydrogenbonding interactions.Remarkably,the detection limit for melamine was as low as 2.4 ppb,providing a highly sensitive and efficient approach for the visual detection of melamine.
基金supported by a grant from the National Nat-ural Science Foundation of China(No.21472176).
文摘The asymmetric carbenoid C–H insertion of 3-diazooxindoles into 1,4-cyclohexadiene has been accomplished in the presence of chiral bis(imidazoline) NCN pincer iridium(Ⅲ) complexes as the catalysts. With a catalyst loading of 0.5 mol%, the reactions proceeded smoothly at 0℃ to afford a variety of chiral 3-substituted oxindoles in good yields with moderate to excellent enantioselectivities(up to 99% ee). The protocol exhibits good functional group tolerance with respect to 3-diazooxindoles and is readily scaled up to 2 mmol scale without any loss in activity and enantioselectivity. Density functional theory(DFT)calculations have been performed to better understand the reaction mechanism and to explain the stereochemical outcome of the reactions.
基金the financial support from the NSFC(22061006)Key Laboratory of Applied Surface and Colloid Chemistry(Shaanxi Normal University)of Ministry of Education,Natural Science Basic Research Plan in Shaanxi Province of China(No.2024JC-YBMS-119)+1 种基金Key Research and Development Plan Project of Xianyang(L2023-ZDYF-QYCX-030)Guizhou Provincial Basic Research Program(GCC[2023]078,ZK[2023]043,ZK[2022]144).
文摘Comprehensive Summary Terpyridine ligands have been applied as a class of unique ligands due to their rich coordination chemistry in the catalysis.Herein,we developed a new class of C_(2)-symmetric chiral terpyridine-pyrroloimidazolone ligands(TPy-BPI).Their catalytic activity was evaluated in the asymmetric Friedel-Crafts alkylation of indoles with 2,3-dioxopyrrolidines.Excellent yields(up to 92%)and high enantioselectivities(up to 97%ee)are obtained for a wide range of substrates under mild conditions.
基金supported by the National Natural Science Foundation of China (20674081,20934006) the Ministry of Science and Technology of China (2005CB623802,2009AA03Z501).
文摘The aryldiimine NCN-pincer stabilized neodymium dichloride combined with aluminum alkyls established a new type of homogeneous binary neutral Ziegler-Natta catalyst system.This system exhibited high activity and high cis-1,4 selectivity for the polymerization of isoprene (Tp=20 °C,98.2%;Tp=-20 °C,】 99%).Such catalytic performances remained under a broad range of polymerization temperatures and monomer-to-neodymium ratios (from 500 to 8000),reaching high number-average molecular weight (Mn=1582 kg/mol) and relatively narrow molecular weight distribution (PDI=1.68),which was,however,influenced by the amount and bulkiness of aluminum alkyls.Dynamic investigation of the polymerization was performed,which showed the number-average molecular weight of the resultant polyisoprene had an almost linear correlation with the conversion,suggesting,in some degree,the polymerization with this catalytic system was controllable.
基金This work was supported by the National Natural Science Foundation of China(21502080,21772076,21871117,21772071,21702136,91956203)the“111”Program of Ministry of Education of China,the Major Project(2018ZX09711001-005-002)of Ministry of Science and Technology of China+2 种基金the Science and Technology Commission of Shanghai Municipality(19IC1430100)This work was supported by the High-Performance Computing Center of Shanghai Jiao Tong UniversityAlso,we thank Prof.Qing-Wei Zhang from the University of Science and Technology of China for his helpful discussion.
文摘A new type of dianionic Ir(Ⅲ) CCC pincer complexes(SNHC-Ir, 1a–1c) is successfully designed and synthesized by developing a one-step methodology, which involves an initial coordination of Ir(I) with the NHC and subsequent metallation of double sp2C–H bonds. This method is considerably useful over those reported by using strong coordination ligand or carbonic anion exchange,and would provide an alternative efficient template of organometallics synthesis. Experimental and density functional theory(DFT) calculation results indicate that the spirocyclic framework is a favourable factor for the facile formation and stabilization of these complexes. Primary investigation shows that chloride 1b can well catalyze homo and hetero addition of styrene derivatives and remote olefin isomerization, which represents the first catalytic application of the dianionic CCC pincer complexes.
基金supported by the National Basic Research Program (2012CB215306)the National Natural Science Foundation of China (21325208, 21361140372, 21572212)+2 种基金Chinese Academy of Sciences (KFJ-EW-STS-051)Fundamental Research Funds for the Central Universities (WK2060190025)Scientific research funds of Anhui University (J10117700074)
文摘Extracting hydrogen from methanol is a safe and cost-efficient strategy for fuel supply. This process was realized recently at a mild condition with excellent efficiency by ruthenium pincer catalysts. Despite the experimental success, the associated mechanism remains under debate. With the aid of density functional theory(DFT) calculations, an updated and self-consistent mechanism which involves Me OH-catalysed dehydrogenation of ruthenium hydride intermediate and pre-protonation of the pincer ligand was present herein. This mechanism is kinetically favoured over the previously-proposed water- or formic- acid-participated ones and more consistent with the optimal experimental condition where strong base and neat methanol solvent are used.
基金supported by Shenzhen Nobel Prize Scientists Laboratory Project(C17783101)Shenzhen YOUWEI Tech Group,Guangdong Provincial Key Laboratory of Catalysis(2020B121201002)+2 种基金the Natural Science Foundation of Guangdong Province(2021A1515010329)the National Natural Science Foundation of China(22171128)Shenzhen Science and Technology Program(KQTD20180411143514543,JCYJ20190809143611743)。
文摘The asymmetric reduction of carbonyl compounds by means of the Ru-chiral diphosphine-chiral diamine catalysts is widely useful in organic synthesis where high levels of enantioselectivities have been attributed to multiple ligand chiral elements as well as essential stereochemical matching synergies within them.Described here is the design and discovery of new pincer-type Ru-catalysts that feature only single stereogenic element within ligands,yet the such significantly simplified structure is demonstrated to be well competent for effecting asymmetric reductions as well as kinetic resolutions over a broad range of highly functionalized ketones/alcohols,including heteroaryl substituted substrates that were challenging by known catalyst systems.Alcohols were furnished not only in excellent enantioselectivities,but with turnover numbers(up to 100,000 TONs)that reach the highest levels known to date in asymmetric transfer hydrogenation of ketones.This work should help shed light on the intricate origin of enantioselection in these important processes,and further stimulate rational understanding as well as optimization of chiral catalysts towards efficiency and simplicity.
基金supported by the National Natural Science Foundation of China (Grant No. 50635030)
文摘The mineral phases and structure of pincer for the freshwater lobster were analyzed and observed by using X-ray diffraction and field-emission scanning electronic microscope with energy dispersive spectroscopy, and the mechanical properties of pincer were determined by using nano-indenter and micro-tribometer. The results showed that the pincers contained Ca, Mg, C, O, Na, etc. elements and there were many amorphous mineral phases in the lobster pincers. There were many concave hollows and convex domes with seta on the surface of pincer, and some spines were observed on the surface of seta, which exhibited non-smooth surface. The exoskeleton of pincer consisted of epicuticle, exocuticle and endocuticle, and the microstructure of exocuticle and endocuticle displayed the twisted plywood structure with chitin protein fibers. The mean hardness and elastic modulus on the surface of fresh pincers were 0.27 GPa and 5.28 GPa, respectively. With the increase in distance from the surface, the hardness and elastic modulus all decreased gradually. This indicated that the transition of hardness and elastic modulus occurred from exocuticle to endocuticle. When the heat treatment temperature was lower than 200°C, the values of hardness and elastic modulus fluctuated slightly, while they increased at the temperature beyond 200°C. As the pincers slid against Si3N4 balls in water and air, the friction coefficients in water were higher than those in air. The research could provide a bio-inspired basis for the structural design of composite materials and anti-friction surface.
基金Financial support from the National Natural Science Foundation of China(grant nos.21871059 and 21861132002)the National Key R&D Program of China(grant no.2016YFA0202902)Department of Chemistry,Fudan University are gratefully acknowledged.
文摘Considering the importance of the valorization of CO_(2),a number of phosphine-containing ruthenium pincer complexes have been successfully heterogenized using a“direct knitting”strategy without any premodification.The resulting porous organometallic polymers(POMPs)with high specific-surface areas,hierarchical pores,and uniformly dispersed Ru single-sites exhibited outstanding catalytic activity toward the N-formylation of diverse amines with CO_(2).Besides excellent turnover number(TON,5×10^(5))and turnover frequency(TOF,5592 h-1),the obtained formamides were readily hydrogenated to methanol with the same catalyst.Consequently,an amine-assisted direct hydrogenation system of CO_(2)to methanol was established by POMPs with higher activity and TON(1.46×10^(4))than their molecular precursors,shedding light on the direct valorization of CO_(2)and carbon neutral recycling.
文摘The reactions of a variety of 4,6-dimethyl-1,3-bis(imino)benzenes 2a-g derived from 4,6-dimethylisophthalaldehyde and anilines or benzylamine with palladium(II)acetate in anhydrous acetic acid under nitrogen were investigated.Experiment results demonstrate that cyclopalladations in such condition are applicable not only to the present system under study but also to the 5-substituted bis(imino)benzenes 6,7.The molecular structure of 3b was further confirmed by X-Ray single-crystal diffraction.3b Crystallizes in orthorhombic,space group P2(1)2(1)2(1)with a=0.734 53(8),b=1.683 8(3),c=1.691 7(2)nm,α=β=γ=90°.Treatment of 2b with K2PtCl4in anhydrous acetic acid affords the corresponding NCN-platinum pincer.Carbon-carbon cross coupling reactions catalyzed with 3b were investigated.These palladium complexes have been proved to be high effective catalysts for Suzuki coupling reaction.
