The title complex N,O-bis{[2-[(2,4-dimethylphenyl)imino]-5-methoxyl]-phenol}-palladium(Ⅱ)(CC_(32)H_(32)N_2O_4Pd) has been synthesized by the reaction of 2-[(2,4-dimethylphenyl)imino]-5-methoxyl-phenol wit...The title complex N,O-bis{[2-[(2,4-dimethylphenyl)imino]-5-methoxyl]-phenol}-palladium(Ⅱ)(CC_(32)H_(32)N_2O_4Pd) has been synthesized by the reaction of 2-[(2,4-dimethylphenyl)imino]-5-methoxyl-phenol with Pd(CH_3COO)_2,and characterized by elemental analysis,IR spectrum and single-crystal X-ray diffraction analysis.The crystal belongs to the monoclinic system,space group P2_1/c with a = 12.058(2),b = 8.3624(17),c = 14.735(3) ?,β = 107.66(3)°,V = 1415.7(5)?~3,C_(32)H_(32)N_2O_4Pd,Mr = 615,Z = 2,D_c = 1.443 Mg/m^3,μ = 0.695 mm^(-1),F(000) = 632,T = 293(2) K,the final R = 0.0514 and w R = 0.1356(I 〉 2s(I)).Under the co-catalysis of methylaluminoxane(MAO),the palladium compound exhibited favorable catalytic activity for the polymerization of norbornene(NB).展开更多
The title complex[Zn_2L(C_5H_7N_2)_2(C_5H_7N_2·HClO_4)_2](L=1,2-di(3', 5'-dimethylpyrazolyl) formylhydrazine and C_5H_7N_2= 3 , 5 dimethylpyrazole anion) has been synthesized by template reaction, in whic...The title complex[Zn_2L(C_5H_7N_2)_2(C_5H_7N_2·HClO_4)_2](L=1,2-di(3', 5'-dimethylpyrazolyl) formylhydrazine and C_5H_7N_2= 3 , 5 dimethylpyrazole anion) has been synthesized by template reaction, in which carbonhydrazine, 2, 4-pentanedione and zinc perchlorate hexahydrate were used as the original materials. The crystals of complex with formula C_(32)H_(46)N_(14)O_(10)Cl_2Zn_2 (Mr=988.46) are triclinic,space group P1,a= 8.275 (2),b=11.523 (3),c= 12.872(5), a=69. 90(3),β= 69.79 (2), γ=83. 52 (2)°,V=1081.6(6),Z=1,Dc=1.524g/cm ̄3,μ=13.265cm ̄(-1),F (000)=510. The final refinement is converged with R= 0.057. The results indicate that in one complex molecule there are three kinds of pyrazole rings all directly coordinated to the central Zn atom; and each zinc atom possesses a five-coordinated polyhedron.展开更多
The N,N -(phenyl-2-pyridinylmethylene)-3,3 ,5,5 -tetramethylbenzidine and its dimeric Co(Ⅱ)and Ni(Ⅱ) complexes were synthesized.The organic compound was characterized by elemental analyses,IR and NMR spectra,while t...The N,N -(phenyl-2-pyridinylmethylene)-3,3 ,5,5 -tetramethylbenzidine and its dimeric Co(Ⅱ)and Ni(Ⅱ) complexes were synthesized.The organic compound was characterized by elemental analyses,IR and NMR spectra,while the bimetal complexes were determined by elemental analyses,IR spectra as well as the single-crystal X-ray diffraction.The nickel complex showed high activity for ethylene polymerization and its cobalt analogue showed negligible active in ethylene activation.展开更多
The novel alkaline metal complex Ca(BPDCH)2 (1, BPDCH2 = 2,2'-bipyri- dine-5,5'-dicarboxylic acid) has been synthesized by the hydrothermal reaction of Ca(NO3)2·4H2O with 2,2'-bipyridine-5,5'-dicarboxyl...The novel alkaline metal complex Ca(BPDCH)2 (1, BPDCH2 = 2,2'-bipyri- dine-5,5'-dicarboxylic acid) has been synthesized by the hydrothermal reaction of Ca(NO3)2·4H2O with 2,2'-bipyridine-5,5'-dicarboxylic acid. The molecular and crystal structures of complex 1 have firstly been characterized by FTIR, elemental analysis, and X-ray single-crystal diffraction. The 3D MOF structure of complex 1 was interpreted by the versatile binding modes-the intermolecular hydrogen bonds and π-π stacking interactions of 2,2'-bipyridine-5,5'-dicarboxylic acid ligand. The analysis results show complex 1 belongs to a coordination polymer with 3D MOF structure. The results of thermogravimetric analysis and solubility demonstrate complex 1 is a thermostable compound and does not dissolve in water and traditional organic solvents.展开更多
A series of half-sandwich group IV metal complexes with tridentate monoanionic phenoxy-imine arylsulfide [O-NS] ligand [2-Bu^t4-Me-6-((2-(SC6H5)C6H4N = CHC6H2O)]- (La) and dianionic phenoxy-amine arylsulfide [O...A series of half-sandwich group IV metal complexes with tridentate monoanionic phenoxy-imine arylsulfide [O-NS] ligand [2-Bu^t4-Me-6-((2-(SC6H5)C6H4N = CHC6H2O)]- (La) and dianionic phenoxy-amine arylsulfide [O-N-S] ligand [2-Bu^t4-Me-6-((2-(SC6H5)C6H4N-CH2C6H2O)]2- (Lb) have been synthesized and characterized. Lb was obtained easily in high yield by reduction of ligand La with excess LiAlH4 in cool diethyl ether. Half-sandwich Group Ⅳ metal complexes CpTi[O-NS]Cl2 (1a), CpZr[O-NS]Cl2 (1b), CpTi[O-N-S]Cl (2a), CpZr[O-N-S]Cl (2b) and CpZr[O-N-S]Cl (2c) were synthesized by the reactions of La and Lb with CpTiCl3, CpZrCl3 and Cp ZrCl3, and characterized by IR, ^1H-NMR, ^13C-NMR and elemental analysis. In addition, an X-ray structure analysis was performed on ligand Lb. The title Group IV half-sandwich bearing tridentate [O,N,S] ligands show good catalytic activities for ethylene polymerization in the presence of methylaluminoxane (MAO) as co-catalyst up to 1.58 × 10^7 g-PE.mol-Zr-1.h-1. The good catalytic activities can be maintained even at high temperatures such as 100 ℃ exhibiting the excellent thermal stability for these half-sandwich metal pre-catalysts.展开更多
Binuclear aluminum alkyl complexes 2a–4g supported by linked bis(β-diketiminate) ligands were synthesized via the reaction of AlEt3 or AlMe3 and the corresponding proligand in a 2:1 molar ratio with moderate yiel...Binuclear aluminum alkyl complexes 2a–4g supported by linked bis(β-diketiminate) ligands were synthesized via the reaction of AlEt3 or AlMe3 and the corresponding proligand in a 2:1 molar ratio with moderate yields. The isolated complexes were well-characterized by ^1H-NMR, ^13C-NMR and elemental analysis. The binuclear nature of aluminum complex 2b was further confirmed by an X-ray diffraction study. All complexes 2a–4g could efficiently initiate the ring-opening polymerization(ROP) of ε-caprolactone in toluene. The substituents at the aromatic rings and the linker unit in the auxiliary ligands exerted significant influence on the catalytic behavior of the investigated aluminum complexes. Complex 4g(R^1 = R^2 = Cl) containing propylenyl bridging unit exhibited the highest catalytic activity among these complexes, which might be attributed to the increased electrophilicity of the metal center as well as more opened coordination sphere. The molecular weights of obtained poly(ε-caprolactone)s deviating considerably from the theoretical values indicated that the ROP of ε-caprolactone by complexes 2a–4g was not well-controlled, which was also judged from the broad molecular weight distributions(MWD = 1.47-2.47) of produced poly(ε-caprolactone)s. These complexes proved to be inactive toward the polymerization of rac-lactide alone. In the presence of alcohol the polymerization occurred, which was actually initiated by the decomposition species of the aluminum complex upon the treatment with isopropanol.展开更多
Rare-earth metal dialkyl complexes[1-Bn-3-(DippN=CH)C_(8)H_(4)N]RE(CH_(2)SiMe_(3))2(thf)2(Dipp=2,6-iPr_(2)C_(6)H_(3),RE=Y(1)and Er(2))were prepared through the cyclometalation reactions of the N-Bn-3-imino-functionali...Rare-earth metal dialkyl complexes[1-Bn-3-(DippN=CH)C_(8)H_(4)N]RE(CH_(2)SiMe_(3))2(thf)2(Dipp=2,6-iPr_(2)C_(6)H_(3),RE=Y(1)and Er(2))were prepared through the cyclometalation reactions of the N-Bn-3-imino-functionalized indolyl ligand 1-Bn-3-(DippN=CH)C8H5N with one equivalent of rare-earth metal trialkyl precursors.The structures of compounds 1 and 2 were confirmed by X-ray crystal analyses and characterized by elemental analysis,IR,NMR spectroscopy wherein applicable.In the presence of cocatalysts,these rare-earth metal dialkyl complexes initiated isoprene polymerization with a high activity(95% conversion of 2000 equivalent of isoprene in 360 min),producing polymers with high regioselectivity(1,4-polymers up to 91%).展开更多
Activated by methylaluminoxane, mononuclear bis(hydroxyindanone-iminate)nickel complexes Ni[ArN == CC_2H_3(CH3)C_6H_2(R)O]_2 (Ar = 2,6-i-Pr2C6H3, R = Me (1), R = Cl (2), and R = H (3)) showed good activity for the sty...Activated by methylaluminoxane, mononuclear bis(hydroxyindanone-iminate)nickel complexes Ni[ArN == CC_2H_3(CH3)C_6H_2(R)O]_2 (Ar = 2,6-i-Pr2C6H3, R = Me (1), R = Cl (2), and R = H (3)) showed good activity for the styrene polymerization. The effect of many reaction parameters including the Al/Ni ratio, tempera- ture, and reaction time on catalytic activities of catalytic systems and the molecular weights of the ob- tained polystyrene was ascertained. The highest activity of 1.34×105 g(PS)·mol^(-1)(Ni)·h^(-1) was obtained under the optimum reaction condition. The 13C NMR spectra of the polymers revealed that the polymer was isotactic-rich atactic polystyrene. And the coordination mechanism was confirmed by the analyses of the polymer chain end-groups.展开更多
基金Supported by the Natural Science Foundation of Fujian Province(2010J01026)the Ministry of Education of China(No.208066)+1 种基金the Education Department of Fujian Province(JA07029)the State Key Laboratory of Structural Chemistry(No.20130013)
文摘The title complex N,O-bis{[2-[(2,4-dimethylphenyl)imino]-5-methoxyl]-phenol}-palladium(Ⅱ)(CC_(32)H_(32)N_2O_4Pd) has been synthesized by the reaction of 2-[(2,4-dimethylphenyl)imino]-5-methoxyl-phenol with Pd(CH_3COO)_2,and characterized by elemental analysis,IR spectrum and single-crystal X-ray diffraction analysis.The crystal belongs to the monoclinic system,space group P2_1/c with a = 12.058(2),b = 8.3624(17),c = 14.735(3) ?,β = 107.66(3)°,V = 1415.7(5)?~3,C_(32)H_(32)N_2O_4Pd,Mr = 615,Z = 2,D_c = 1.443 Mg/m^3,μ = 0.695 mm^(-1),F(000) = 632,T = 293(2) K,the final R = 0.0514 and w R = 0.1356(I 〉 2s(I)).Under the co-catalysis of methylaluminoxane(MAO),the palladium compound exhibited favorable catalytic activity for the polymerization of norbornene(NB).
文摘The title complex[Zn_2L(C_5H_7N_2)_2(C_5H_7N_2·HClO_4)_2](L=1,2-di(3', 5'-dimethylpyrazolyl) formylhydrazine and C_5H_7N_2= 3 , 5 dimethylpyrazole anion) has been synthesized by template reaction, in which carbonhydrazine, 2, 4-pentanedione and zinc perchlorate hexahydrate were used as the original materials. The crystals of complex with formula C_(32)H_(46)N_(14)O_(10)Cl_2Zn_2 (Mr=988.46) are triclinic,space group P1,a= 8.275 (2),b=11.523 (3),c= 12.872(5), a=69. 90(3),β= 69.79 (2), γ=83. 52 (2)°,V=1081.6(6),Z=1,Dc=1.524g/cm ̄3,μ=13.265cm ̄(-1),F (000)=510. The final refinement is converged with R= 0.057. The results indicate that in one complex molecule there are three kinds of pyrazole rings all directly coordinated to the central Zn atom; and each zinc atom possesses a five-coordinated polyhedron.
文摘The N,N -(phenyl-2-pyridinylmethylene)-3,3 ,5,5 -tetramethylbenzidine and its dimeric Co(Ⅱ)and Ni(Ⅱ) complexes were synthesized.The organic compound was characterized by elemental analyses,IR and NMR spectra,while the bimetal complexes were determined by elemental analyses,IR spectra as well as the single-crystal X-ray diffraction.The nickel complex showed high activity for ethylene polymerization and its cobalt analogue showed negligible active in ethylene activation.
基金Supported by the National Natural Science Foundation of China(NSFC 21266019,NSFC 21062011)the Natural Science Fundation of Inner Mongolia(20080404MS020)Program for New Century Excellent Talents in University(NCET-08-858)
文摘The novel alkaline metal complex Ca(BPDCH)2 (1, BPDCH2 = 2,2'-bipyri- dine-5,5'-dicarboxylic acid) has been synthesized by the hydrothermal reaction of Ca(NO3)2·4H2O with 2,2'-bipyridine-5,5'-dicarboxylic acid. The molecular and crystal structures of complex 1 have firstly been characterized by FTIR, elemental analysis, and X-ray single-crystal diffraction. The 3D MOF structure of complex 1 was interpreted by the versatile binding modes-the intermolecular hydrogen bonds and π-π stacking interactions of 2,2'-bipyridine-5,5'-dicarboxylic acid ligand. The analysis results show complex 1 belongs to a coordination polymer with 3D MOF structure. The results of thermogravimetric analysis and solubility demonstrate complex 1 is a thermostable compound and does not dissolve in water and traditional organic solvents.
基金financially supported by the Shanghai Science and Technology Committee(08DZ2270500,08DJ1400103)Shanghai Leading Academic Discipline Project(B108)the National Basic Research Program of China(2009CB825300,2010DFA41160)
文摘A series of half-sandwich group IV metal complexes with tridentate monoanionic phenoxy-imine arylsulfide [O-NS] ligand [2-Bu^t4-Me-6-((2-(SC6H5)C6H4N = CHC6H2O)]- (La) and dianionic phenoxy-amine arylsulfide [O-N-S] ligand [2-Bu^t4-Me-6-((2-(SC6H5)C6H4N-CH2C6H2O)]2- (Lb) have been synthesized and characterized. Lb was obtained easily in high yield by reduction of ligand La with excess LiAlH4 in cool diethyl ether. Half-sandwich Group Ⅳ metal complexes CpTi[O-NS]Cl2 (1a), CpZr[O-NS]Cl2 (1b), CpTi[O-N-S]Cl (2a), CpZr[O-N-S]Cl (2b) and CpZr[O-N-S]Cl (2c) were synthesized by the reactions of La and Lb with CpTiCl3, CpZrCl3 and Cp ZrCl3, and characterized by IR, ^1H-NMR, ^13C-NMR and elemental analysis. In addition, an X-ray structure analysis was performed on ligand Lb. The title Group IV half-sandwich bearing tridentate [O,N,S] ligands show good catalytic activities for ethylene polymerization in the presence of methylaluminoxane (MAO) as co-catalyst up to 1.58 × 10^7 g-PE.mol-Zr-1.h-1. The good catalytic activities can be maintained even at high temperatures such as 100 ℃ exhibiting the excellent thermal stability for these half-sandwich metal pre-catalysts.
基金financially supported by the National Natural Science Foundation of China (Nos. 20604009 and 21474028)
文摘Binuclear aluminum alkyl complexes 2a–4g supported by linked bis(β-diketiminate) ligands were synthesized via the reaction of AlEt3 or AlMe3 and the corresponding proligand in a 2:1 molar ratio with moderate yields. The isolated complexes were well-characterized by ^1H-NMR, ^13C-NMR and elemental analysis. The binuclear nature of aluminum complex 2b was further confirmed by an X-ray diffraction study. All complexes 2a–4g could efficiently initiate the ring-opening polymerization(ROP) of ε-caprolactone in toluene. The substituents at the aromatic rings and the linker unit in the auxiliary ligands exerted significant influence on the catalytic behavior of the investigated aluminum complexes. Complex 4g(R^1 = R^2 = Cl) containing propylenyl bridging unit exhibited the highest catalytic activity among these complexes, which might be attributed to the increased electrophilicity of the metal center as well as more opened coordination sphere. The molecular weights of obtained poly(ε-caprolactone)s deviating considerably from the theoretical values indicated that the ROP of ε-caprolactone by complexes 2a–4g was not well-controlled, which was also judged from the broad molecular weight distributions(MWD = 1.47-2.47) of produced poly(ε-caprolactone)s. These complexes proved to be inactive toward the polymerization of rac-lactide alone. In the presence of alcohol the polymerization occurred, which was actually initiated by the decomposition species of the aluminum complex upon the treatment with isopropanol.
基金supported by the Natural Science Foundation of Anhui Province(No.2008085ME174)financial support from Anhui Normal University(FMS201915)。
文摘Rare-earth metal dialkyl complexes[1-Bn-3-(DippN=CH)C_(8)H_(4)N]RE(CH_(2)SiMe_(3))2(thf)2(Dipp=2,6-iPr_(2)C_(6)H_(3),RE=Y(1)and Er(2))were prepared through the cyclometalation reactions of the N-Bn-3-imino-functionalized indolyl ligand 1-Bn-3-(DippN=CH)C8H5N with one equivalent of rare-earth metal trialkyl precursors.The structures of compounds 1 and 2 were confirmed by X-ray crystal analyses and characterized by elemental analysis,IR,NMR spectroscopy wherein applicable.In the presence of cocatalysts,these rare-earth metal dialkyl complexes initiated isoprene polymerization with a high activity(95% conversion of 2000 equivalent of isoprene in 360 min),producing polymers with high regioselectivity(1,4-polymers up to 91%).
基金the National Natural Science Foundation of China (Grant Nos. 20531020, 20721063, and 20771028)Shanghai Leading Academic Discipline Project (Grant No. B108)+1 种基金the National Basic Research Program of China (Grant No. 2005CB623800) Shanghai Science and Technology Committee (Grant No. 06XD14002)
文摘Activated by methylaluminoxane, mononuclear bis(hydroxyindanone-iminate)nickel complexes Ni[ArN == CC_2H_3(CH3)C_6H_2(R)O]_2 (Ar = 2,6-i-Pr2C6H3, R = Me (1), R = Cl (2), and R = H (3)) showed good activity for the styrene polymerization. The effect of many reaction parameters including the Al/Ni ratio, tempera- ture, and reaction time on catalytic activities of catalytic systems and the molecular weights of the ob- tained polystyrene was ascertained. The highest activity of 1.34×105 g(PS)·mol^(-1)(Ni)·h^(-1) was obtained under the optimum reaction condition. The 13C NMR spectra of the polymers revealed that the polymer was isotactic-rich atactic polystyrene. And the coordination mechanism was confirmed by the analyses of the polymer chain end-groups.