The hydroaminomethylation of 1-dodecene catalyzed by water soluble rhodium complex RhCl(CO)(TPPTS)2 in the presence of surfactant CTAB was investigated. High reactivity and selectivity for tertiary amine were achieved...The hydroaminomethylation of 1-dodecene catalyzed by water soluble rhodium complex RhCl(CO)(TPPTS)2 in the presence of surfactant CTAB was investigated. High reactivity and selectivity for tertiary amine were achieved under relatively mild conditions.展开更多
The structure, properties and application to water-soluble coatings of a new complex antimicrobial agent Ag-carboxylmethyl citosan-thiabendazole （Ag-CMCTS-TBZ） prepared from different materiel ratios were reported. ...The structure, properties and application to water-soluble coatings of a new complex antimicrobial agent Ag-carboxylmethyl citosan-thiabendazole （Ag-CMCTS-TBZ） prepared from different materiel ratios were reported. The silver ions were preferably coordinated with the free-NH2 groups and the -OH groups of secondary alcohol and carboxyl in CMCTS. TBZ preferably bonded to carboxyl group in CMCTS by electrostatic force and hydrogen bonding. Increase in silver ions content in the complex agent improved to some limited extent the antibacterial activity, but enhanced coloring and cost of the complex agent. Increase in TBZ content resulted in increase of antifungal activity, but decrease of water solubility of the complex agent. The antimicrobial MICs of the complex agent to Esherichia coil, Staphylococcus aureus, Candida albicans, Aspergillus niger, Mucor sp. were 20 -80, 15 -60, 20 - 55, 40 - 250, and 400 - 1700 mg/kg, respectively. Addition of 0.1% of this complex agent to acrylic emulsion paint made the paint without substantial change in color, luster, viscosity, odor or pH value, but with an excellent and chronically persisting broad-spectra antimicrobial activity.展开更多
The study of nanosecond dynamics of macromolecules with the lumines-cent methods make it possible to investigate the formation and functioning of polymericcomplexes, polymeric conjugates and macromolecular metal compl...The study of nanosecond dynamics of macromolecules with the lumines-cent methods make it possible to investigate the formation and functioning of polymericcomplexes, polymeric conjugates and macromolecular metal complexes, which are widelyused for solving many practical tasks. The nanosecond dynamics of macromolecules are ahighly sensitive indicator of interpolymer complexes (IPC) formation. It enables us to solvethe problems of studying IPC formation and stability and to investigate the interpolymerreactions of exchange and substitution. The investigation of changes in the rotational mo-bility of globular protein molecules as a whole makes it possible to determine the complexcomposition and its stability, and to control the course of polymer-protein conjugate forma-tion reaction. The nanosecond dynamics of polymers interacting with surfacants' ions (S)are the sensitive indicator of the S-polymer complex formation. A method for determin-ing the equilibrium constants of the S-polymer complex formation was developed on thebasis of the study of polymer chains mobility. It is established that nanosecond dynamicsinfluences the course of chemical reactions in polymer chains. Moreover, the marked effectof the nanosecond dynamics is also revealed in the study of photophysical processes (theformation of excimers and energy migration of electron excitation) in polymers with pho-toactive groups. It was found that the efficiency of both processes increases with increasingthe mobility of side chains, the carriers of photoactive groups.展开更多
The hydrosilylation of alkenes with triethoxysilane has been achieved at 120 C in the presence of 0.01 mol%of thioetherfunctionalized MCM-41 anchored rhodium complex,affording the corresponding addition products in 68...The hydrosilylation of alkenes with triethoxysilane has been achieved at 120 C in the presence of 0.01 mol%of thioetherfunctionalized MCM-41 anchored rhodium complex,affording the corresponding addition products in 68-91%yields.This supported rhodium complex can be reused several times without noticeable loss of activity.Our system not only solves the basic problems of catalyst separation and recovery,but also avoids the use of phosphine ligands.展开更多
The catalytic performances of four HRh(CO)(PPh3)3-diphosphine (BISBI,BDPX, BDNA and BINAP) systems in 1-dodecene hydroformylation were investigated and compared with HRh(CO)(PPh3)3-PPh3 system. The catalyst system HR...The catalytic performances of four HRh(CO)(PPh3)3-diphosphine (BISBI,BDPX, BDNA and BINAP) systems in 1-dodecene hydroformylation were investigated and compared with HRh(CO)(PPh3)3-PPh3 system. The catalyst system HRh(CO)(PPh3)3-BISBI exhibited very high regioselectivity for the formation of linear aldehyde.展开更多
Vibrational and H-NMR spectroscopic studies on di-μ-chlorobis(1,5-cyclooctadiene) of iridium(I) and rhodium (I) complexes have been carried out. In addition, the two D2h and D2 structures for both complexes have been...Vibrational and H-NMR spectroscopic studies on di-μ-chlorobis(1,5-cyclooctadiene) of iridium(I) and rhodium (I) complexes have been carried out. In addition, the two D2h and D2 structures for both complexes have been fully optimized. It was expected from the single-molecule vapor-phase density functional theory (DFT) calculation that the D2 structure is more stable by 5 - 6 kcal/mol. While spectroscopic analysis study confirms that in the solid phase, the two complexes retain the higher D2h symmetry. The vibrational wavenumbers of certain modes associated to free 1,5-cyc- looctadiene were observed to be shifted to lower values upon coordination with rhodium or iridium metals. It was also found theoretically that the metal-olefin interaction is slightly more pronounced for iridium metal.展开更多
Treatment of 1,3-di- t -butylcyclopentadiene with rhodium trichloride in EtOH leads to the formation of binuclear half-sandwich complex [Cp t RhCl( μ -Cl)] 2 (1) (Cp t = η 5- t Bu 2C 5H 3) which reacts with trimethy...Treatment of 1,3-di- t -butylcyclopentadiene with rhodium trichloride in EtOH leads to the formation of binuclear half-sandwich complex [Cp t RhCl( μ -Cl)] 2 (1) (Cp t = η 5- t Bu 2C 5H 3) which reacts with trimethylphosphine to give Cp t Rh(PMe 3)Cl 2(2) in high yield. 2 reacts with ammonium polysulfide, (NH 4) 2S x to give cyclooligosulfido half-sandwich complexes Cp t Rh(PMe 3)(S n )( n =4(4a),6(4b)). Desulfurization of 4b by excess PPh 3 results in cyclotetrasulfido product 4a, while 4a takes up sulfur from polysulfide to convert cyclohexasulfido product 4b. The reaction of 2 with Et 4NI gives diiodide complex 3 which is determined by single crystal X-ray crystallographic analysis.展开更多
A highly efficient and selective[2+2+2]cyclization of diynes and monoalkynes was catalyzed by rhodium under room temperature in water/THF mixed solvent,affording isoindolines and isobenzofurans in good to excellent yi...A highly efficient and selective[2+2+2]cyclization of diynes and monoalkynes was catalyzed by rhodium under room temperature in water/THF mixed solvent,affording isoindolines and isobenzofurans in good to excellent yields.The center atoms (N,O) in the diynes showed a significant effect for the cyclization.展开更多
The complex [（CF3-BINAP（O））Rh（COD）][ClO4]·Et2O （2, CFa-BINAP（O） = 2- {bis[3,5-bis（trifluoromethyl）phenyl]phosphino } -2 ＇- {bis [3,5-bis（trifluoromethyl）phenyl]phosphinyl } -1,1、-binaphthyl, COD = ...The complex [（CF3-BINAP（O））Rh（COD）][ClO4]·Et2O （2, CFa-BINAP（O） = 2- {bis[3,5-bis（trifluoromethyl）phenyl]phosphino } -2 ＇- {bis [3,5-bis（trifluoromethyl）phenyl]phosphinyl } -1,1、-binaphthyl, COD = 1,5-cyclooctadiene） was obtained directly from the reaction of CF3- BINAP（O） ligand with [Rh（COD）][C104]. Complex 2 has been characterized by single-crystal X-ray diffraction. The crystal adopts space group P21/n with a = 19.0727（4）, b = 15.6275（4）, c = 22.3039（6） A, fl = 112.3570（10）°, V= 6148.2（3） A3, Z = 4, Dc = 1.693 g/cm3, F（000） = 3144, μ（MoKa） = 0.500 mm-1, the final R = 0.0947 and wR = 0.2501. Structural studies reveal that Rh（I） is coordinated by one oxygen and one phosphorus in the same ligand. Asymmetric hydrogenation of acetami- docinnamic acid with compound 2 was also evaluated.展开更多
The highly water-soluble phosphine ligands Na2O3PCH2CH2NH(CH2CH2O)nCH2CH2N- (CH2PPh2)2 (n=1,2,3) were prepared by a new and simple route under mild conditions in good yield; the palladium (II) complexes of the ligands...The highly water-soluble phosphine ligands Na2O3PCH2CH2NH(CH2CH2O)nCH2CH2N- (CH2PPh2)2 (n=1,2,3) were prepared by a new and simple route under mild conditions in good yield; the palladium (II) complexes of the ligands 3a~c with 2:1 or 4:1 -PPh2 to Pd2+ molar ratio were also prepared and characterized .展开更多
A silica-supported poly-γ- aminopropylsiloxane-rhodium-cobalt bimetallic complex(abbreviated as SiO_2-NH_2-Rh-Co)has been prepared and used as catalyst for hydroformylationof methyl methacrylate. The results showed t...A silica-supported poly-γ- aminopropylsiloxane-rhodium-cobalt bimetallic complex(abbreviated as SiO_2-NH_2-Rh-Co)has been prepared and used as catalyst for hydroformylationof methyl methacrylate. The results showed that the catalyst could catalyze the reaction in95.6% conversion with 92.8% selectivity for the normal aldehyde, methyl β-formylisobu-tyrate. Such catalyst also showed high stability during the reaction and could be used repeat-edly.展开更多
Water-soluble copolymers of p-methacrylamidobenzoic acid(MABA)with neutral comonomers(N-vinylpyrrolidone(VP),N-methyl-N-vinylacetamide(MVAA),N-methacryloyl glucosamine(MAG))and anionic comononer sodium styrene sulfona...Water-soluble copolymers of p-methacrylamidobenzoic acid(MABA)with neutral comonomers(N-vinylpyrrolidone(VP),N-methyl-N-vinylacetamide(MVAA),N-methacryloyl glucosamine(MAG))and anionic comononer sodium styrene sulfonate(NaSS)were synthesized by radical copolymerization.The interactions between the prepared copolymers and Tb^(3+)ions in aqueous solutions were studied;the significant influence of chemical structure of a comonomer on luminescence intensity of Tb^(3+)complexes with the copolymers was revealed.The luminescence intensity of Tb^(3+)complexes with the copolymers containing N-vinylamide units(VP,MVAA)is three times more intense than that observed for the complexes between Tb^(3+)and MAG-containing copolymers.In the case of NaSS-containing copolymers,the luminescence intensity is controlled by the values of binding constants between Tb^(3+)and MABA and the content of MABA units in a copolymer.The studied copolymers and their complexes with Tb^(3+)have low cytotoxicity and a pronounced antiviral activity against human respiratory syncytial virus.展开更多
At present, using cyclodextrins or cyclodextrin derivatives with suitable internal annular dimension to embed C60 so as to form inclusion complexes has been one of the main ways to improve C60＇s water-solubility. In ...At present, using cyclodextrins or cyclodextrin derivatives with suitable internal annular dimension to embed C60 so as to form inclusion complexes has been one of the main ways to improve C60＇s water-solubility. In three kinds of cyclodextrins (α-, β-, γ-CD), only γ-CD has cavity large enough to include C60 whereas α-, and β-CD have not. In the case of DMβCD, the "out-stretching" methyl groups enlarge the cavity so that it can include C60. Starting from the same thought, we use epichlorohydrin crosslinked展开更多
文摘The hydroaminomethylation of 1-dodecene catalyzed by water soluble rhodium complex RhCl(CO)(TPPTS)2 in the presence of surfactant CTAB was investigated. High reactivity and selectivity for tertiary amine were achieved under relatively mild conditions.
文摘The structure, properties and application to water-soluble coatings of a new complex antimicrobial agent Ag-carboxylmethyl citosan-thiabendazole （Ag-CMCTS-TBZ） prepared from different materiel ratios were reported. The silver ions were preferably coordinated with the free-NH2 groups and the -OH groups of secondary alcohol and carboxyl in CMCTS. TBZ preferably bonded to carboxyl group in CMCTS by electrostatic force and hydrogen bonding. Increase in silver ions content in the complex agent improved to some limited extent the antibacterial activity, but enhanced coloring and cost of the complex agent. Increase in TBZ content resulted in increase of antifungal activity, but decrease of water solubility of the complex agent. The antimicrobial MICs of the complex agent to Esherichia coil, Staphylococcus aureus, Candida albicans, Aspergillus niger, Mucor sp. were 20 -80, 15 -60, 20 - 55, 40 - 250, and 400 - 1700 mg/kg, respectively. Addition of 0.1% of this complex agent to acrylic emulsion paint made the paint without substantial change in color, luster, viscosity, odor or pH value, but with an excellent and chronically persisting broad-spectra antimicrobial activity.
基金This work is partly supported by the Russian Foundation of Fundamental Research Grant N 97-03-32682).
文摘The study of nanosecond dynamics of macromolecules with the lumines-cent methods make it possible to investigate the formation and functioning of polymericcomplexes, polymeric conjugates and macromolecular metal complexes, which are widelyused for solving many practical tasks. The nanosecond dynamics of macromolecules are ahighly sensitive indicator of interpolymer complexes (IPC) formation. It enables us to solvethe problems of studying IPC formation and stability and to investigate the interpolymerreactions of exchange and substitution. The investigation of changes in the rotational mo-bility of globular protein molecules as a whole makes it possible to determine the complexcomposition and its stability, and to control the course of polymer-protein conjugate forma-tion reaction. The nanosecond dynamics of polymers interacting with surfacants' ions (S)are the sensitive indicator of the S-polymer complex formation. A method for determin-ing the equilibrium constants of the S-polymer complex formation was developed on thebasis of the study of polymer chains mobility. It is established that nanosecond dynamicsinfluences the course of chemical reactions in polymer chains. Moreover, the marked effectof the nanosecond dynamics is also revealed in the study of photophysical processes (theformation of excimers and energy migration of electron excitation) in polymers with pho-toactive groups. It was found that the efficiency of both processes increases with increasingthe mobility of side chains, the carriers of photoactive groups.
基金National Natural Science Foundation of China(No.20862008)Natural Science Foundation of Jiangxi Province(No.2008GQH0034) for financial support
文摘The hydrosilylation of alkenes with triethoxysilane has been achieved at 120 C in the presence of 0.01 mol%of thioetherfunctionalized MCM-41 anchored rhodium complex,affording the corresponding addition products in 68-91%yields.This supported rhodium complex can be reused several times without noticeable loss of activity.Our system not only solves the basic problems of catalyst separation and recovery,but also avoids the use of phosphine ligands.
基金We thank the National Basic Research Project of China(G2000048008)for the financial support.
文摘The catalytic performances of four HRh(CO)(PPh3)3-diphosphine (BISBI,BDPX, BDNA and BINAP) systems in 1-dodecene hydroformylation were investigated and compared with HRh(CO)(PPh3)3-PPh3 system. The catalyst system HRh(CO)(PPh3)3-BISBI exhibited very high regioselectivity for the formation of linear aldehyde.
文摘Vibrational and H-NMR spectroscopic studies on di-μ-chlorobis(1,5-cyclooctadiene) of iridium(I) and rhodium (I) complexes have been carried out. In addition, the two D2h and D2 structures for both complexes have been fully optimized. It was expected from the single-molecule vapor-phase density functional theory (DFT) calculation that the D2 structure is more stable by 5 - 6 kcal/mol. While spectroscopic analysis study confirms that in the solid phase, the two complexes retain the higher D2h symmetry. The vibrational wavenumbers of certain modes associated to free 1,5-cyc- looctadiene were observed to be shifted to lower values upon coordination with rhodium or iridium metals. It was also found theoretically that the metal-olefin interaction is slightly more pronounced for iridium metal.
基金Financial support by the National Natural Science Foundation of China and by the Special Funds for Major State Basic Research Projects(G1999064800)is gratefully acknowledged.
文摘Treatment of 1,3-di- t -butylcyclopentadiene with rhodium trichloride in EtOH leads to the formation of binuclear half-sandwich complex [Cp t RhCl( μ -Cl)] 2 (1) (Cp t = η 5- t Bu 2C 5H 3) which reacts with trimethylphosphine to give Cp t Rh(PMe 3)Cl 2(2) in high yield. 2 reacts with ammonium polysulfide, (NH 4) 2S x to give cyclooligosulfido half-sandwich complexes Cp t Rh(PMe 3)(S n )( n =4(4a),6(4b)). Desulfurization of 4b by excess PPh 3 results in cyclotetrasulfido product 4a, while 4a takes up sulfur from polysulfide to convert cyclohexasulfido product 4b. The reaction of 2 with Et 4NI gives diiodide complex 3 which is determined by single crystal X-ray crystallographic analysis.
文摘A highly efficient and selective[2+2+2]cyclization of diynes and monoalkynes was catalyzed by rhodium under room temperature in water/THF mixed solvent,affording isoindolines and isobenzofurans in good to excellent yields.The center atoms (N,O) in the diynes showed a significant effect for the cyclization.
基金Supported by the National Natural Science Foundation of China(20972159)
文摘The complex [（CF3-BINAP（O））Rh（COD）][ClO4]·Et2O （2, CFa-BINAP（O） = 2- {bis[3,5-bis（trifluoromethyl）phenyl]phosphino } -2 ＇- {bis [3,5-bis（trifluoromethyl）phenyl]phosphinyl } -1,1、-binaphthyl, COD = 1,5-cyclooctadiene） was obtained directly from the reaction of CF3- BINAP（O） ligand with [Rh（COD）][C104]. Complex 2 has been characterized by single-crystal X-ray diffraction. The crystal adopts space group P21/n with a = 19.0727（4）, b = 15.6275（4）, c = 22.3039（6） A, fl = 112.3570（10）°, V= 6148.2（3） A3, Z = 4, Dc = 1.693 g/cm3, F（000） = 3144, μ（MoKa） = 0.500 mm-1, the final R = 0.0947 and wR = 0.2501. Structural studies reveal that Rh（I） is coordinated by one oxygen and one phosphorus in the same ligand. Asymmetric hydrogenation of acetami- docinnamic acid with compound 2 was also evaluated.
文摘The highly water-soluble phosphine ligands Na2O3PCH2CH2NH(CH2CH2O)nCH2CH2N- (CH2PPh2)2 (n=1,2,3) were prepared by a new and simple route under mild conditions in good yield; the palladium (II) complexes of the ligands 3a~c with 2:1 or 4:1 -PPh2 to Pd2+ molar ratio were also prepared and characterized .
文摘A silica-supported poly-γ- aminopropylsiloxane-rhodium-cobalt bimetallic complex(abbreviated as SiO_2-NH_2-Rh-Co)has been prepared and used as catalyst for hydroformylationof methyl methacrylate. The results showed that the catalyst could catalyze the reaction in95.6% conversion with 92.8% selectivity for the normal aldehyde, methyl β-formylisobu-tyrate. Such catalyst also showed high stability during the reaction and could be used repeat-edly.
基金The work was carried out as part of a State Assignment 12212100171-8.
文摘Water-soluble copolymers of p-methacrylamidobenzoic acid(MABA)with neutral comonomers(N-vinylpyrrolidone(VP),N-methyl-N-vinylacetamide(MVAA),N-methacryloyl glucosamine(MAG))and anionic comononer sodium styrene sulfonate(NaSS)were synthesized by radical copolymerization.The interactions between the prepared copolymers and Tb^(3+)ions in aqueous solutions were studied;the significant influence of chemical structure of a comonomer on luminescence intensity of Tb^(3+)complexes with the copolymers was revealed.The luminescence intensity of Tb^(3+)complexes with the copolymers containing N-vinylamide units(VP,MVAA)is three times more intense than that observed for the complexes between Tb^(3+)and MAG-containing copolymers.In the case of NaSS-containing copolymers,the luminescence intensity is controlled by the values of binding constants between Tb^(3+)and MABA and the content of MABA units in a copolymer.The studied copolymers and their complexes with Tb^(3+)have low cytotoxicity and a pronounced antiviral activity against human respiratory syncytial virus.
基金Project supported by the Doctoral Fund of China and the Science Fund of the Chinese Academy of Sciences.
文摘At present, using cyclodextrins or cyclodextrin derivatives with suitable internal annular dimension to embed C60 so as to form inclusion complexes has been one of the main ways to improve C60＇s water-solubility. In three kinds of cyclodextrins (α-, β-, γ-CD), only γ-CD has cavity large enough to include C60 whereas α-, and β-CD have not. In the case of DMβCD, the "out-stretching" methyl groups enlarge the cavity so that it can include C60. Starting from the same thought, we use epichlorohydrin crosslinked
