The reaction of MeCpLnCl·2LiCl·nTHF with 2 equivalent of LiNPh_2 in THF,hexane and toluene mixture solution gives the new complex[Li(DME)_2][(η~5-MeCp)Ln(NPh_2)_3](Ln=La,Pr,Nd)by extraction with DME.They ha...The reaction of MeCpLnCl·2LiCl·nTHF with 2 equivalent of LiNPh_2 in THF,hexane and toluene mixture solution gives the new complex[Li(DME)_2][(η~5-MeCp)Ln(NPh_2)_3](Ln=La,Pr,Nd)by extraction with DME.They have been characterized by elemental analysis,IR and NMR.The La complex crystallizes in the monoclinic space group P2_1/c with α=1.8335(6)nm,b=1.6576(5)nm,c=1.7461(6)nm, β=96.04°,V=5.277 nm^2,Z=4,D_c=1.26g·cm^(-3),R=0.057 and R_w=0.048(1≥2.5σ(I_o))for 3378 reflec- tions.The complex consists of a pair of a cation and an anion.La^(3+) is coordinated by one methylcyclopentadienyl and three diphenylamidos to form six-coordinate pseudotetrahedron with the mean Ln-N and La-C(ring)distances of 0.2459(8)and 0.2843(11)nm,respectively.展开更多
The lanthanide Schiff base complex [2-OC6H4CHN(2,6-i-Pr2C6H3)]2ErCl(THF) (C42H52ClErN2O3) has been prepared by the reaction of anhydrous LnCl3 with 2 equiv. of the sodium salt of the bidentate Schiff base N-(2,6-diiso...The lanthanide Schiff base complex [2-OC6H4CHN(2,6-i-Pr2C6H3)]2ErCl(THF) (C42H52ClErN2O3) has been prepared by the reaction of anhydrous LnCl3 with 2 equiv. of the sodium salt of the bidentate Schiff base N-(2,6-diisopropylphenyl)salicylaldimine in THF. The crystal structure was determined by X-ray diffraction analysis. The crystal belongs to triclinic, space group P1 with a = 9.200(1), b = 13.637(2), c = 16.705(2) ? a = 74.493(7), b = 77.979(8), g = 81.306(8), V = 1965.2(4) ?, Z = 2, Mr = 835.60, Dc = 1.412 g/cm3, F(000) = 854, T = 193 K, l(MoKa) = 0.7107 ?and m = 22.38 cm-1. The final R = 0.052 and wR = 0.076 for 8386 observed reflections with I ≥ 2s(I).展开更多
The lanthanide complexes containing a bulky tridentate [N,N,O] Schiff base ligand 3,5-But2-2-（OH）C6H2CH=N-8-C9H6N （HL） were synthesized and characterized. The reaction of anhydrous LnCl3 with NaL formed in situ in...The lanthanide complexes containing a bulky tridentate [N,N,O] Schiff base ligand 3,5-But2-2-（OH）C6H2CH=N-8-C9H6N （HL） were synthesized and characterized. The reaction of anhydrous LnCl3 with NaL formed in situ in a 1：1 molar ratio in THF at room temperature afforded the lanthanide Schiff base dichloride complexes LnLCl2（DME） （Ln=Eu （1）; Sm （2））. Complexes 1 and 2 can be used as precursors for the synthesis of the lanthanide cyclopentadienyl Schiff base derivatives. The reactions of complexes 1 and 2 with one equiv of NaCH3C5H4 in THF provided the desired products LnL（CH3C5H4）CI（THF）.THF （Ln=Eu （3）; Sm （4）） in good isolated yields. These complexes were characterized by elemental analysis, IR spectra, and X-ray structural determination, in the case of complexes 3 and 4. The crystal data of complex 3 are monoclinic, P21/C space group, a=1.3370（2） nm, b=1.5190（2） nm, c=1.8910（3） nm, β=109.846（4）°, V=3.6125（8） nm^3, Z=4, Dc=1.416 mg/m^3,μ=1.847 mm^-1, F（000）=1584, R=0.0707, wR=0.1350. The crystal data of complex 4 are monoclinic, P21/c space group, a=1.3383（1） nm, b=1.5210（2） nm, c=1.8960（2） nm, β =109.878（3）°, V=3.6293（7） nm^3, Z=4, Dc=1.407 mg/m^3, μ=1.728 mm^-1, F（000）= 1580, R=0.0670, wR=0.1385.展开更多
Reaction of anhydrous ytterbium trichlorides with 2 equiv. of cyclopentylindenyl lithium in THF solution, followed by removal of the solvent and crystallization of the product from diethyl ether, affords a crystal com...Reaction of anhydrous ytterbium trichlorides with 2 equiv. of cyclopentylindenyl lithium in THF solution, followed by removal of the solvent and crystallization of the product from diethyl ether, affords a crystal complex of the composition (C 5H 9C 9H 6) 2Yb( μ Cl) 2Li(Et 2O) 2. Crystallographic analysis shows that the ytterbium coordinated by two cyclopentylindenyl rings and lithium surrounded by two ether molecules are bridged by the two chlorine atoms and Yb, Li and two chlorine atoms form a plane.展开更多
Two new 15-membered functionalized macrocycles, dioxo^polyazacycloalkanes with three pendant acetato groups, have been synthesized by the condensation reaction of DTPA dianhydride (DTPA=diethylenetriaminepentaacetic a...Two new 15-membered functionalized macrocycles, dioxo^polyazacycloalkanes with three pendant acetato groups, have been synthesized by the condensation reaction of DTPA dianhydride (DTPA=diethylenetriaminepentaacetic acid) with 1,2-diaminopropane, (15-DTPA-1,2-pn), or 1,2-diaminocyclohexane, (15-DTPA-1,2-cy). Their lanthanide complexes [Ln(15-DTPA-1,2-pn)(H 2O)] 2 [Ln=Eu (1), Gd (2)] and [Ln(15-DTPA-1,2-cy)(H 2O)] 2 [Ln=Eu (3), Gd (4)] were also prepared. Single crystal X-ray diffraction analyses of complexes 2 and 4 show that they have dimeric structures in solid state; each metal ion is nine-coordinated in a distorted tricapped-trigonal prism. In complex 4, the coexistence of two diastereoisomeric molecules in the crystal lattice was observed.展开更多
Anhydrous LnCl 3 reacts with 2 equiv. of the sodium salt of the bidentate Schiff base N (2,6 diisopropylphenyl)salicylaldimine in THF to form the monomeric lanthanide chlorides [2 OC 6H 4CH= N(2,6 i P...Anhydrous LnCl 3 reacts with 2 equiv. of the sodium salt of the bidentate Schiff base N (2,6 diisopropylphenyl)salicylaldimine in THF to form the monomeric lanthanide chlorides [2 OC 6H 4CH= N(2,6 i Pr 2C 6H 3) ] 2LnCl(THF) [Ln=Yb (1), Er (2)]. Complex 1 crystallizes in P 1 space group with a =0 9215(2) nm, b = 1 36612(4) nm, c =1 6899(2) nm, α =74 83(3)°, β = 77 43(2)°, γ =81 04(1)°, Z =2, V =1 9929(4) nm 3, D c=1 402 g/cm 3. The two complexes exhibited fairly good catalytic activity in the ring opening polymerization of ε caprolactone.展开更多
Reaction of anhydrous YbCl3 with 1 equiv. of LLi [L=p-ClPhNC(Me)CH(Me)N(C6H3-2,6-i-Pr2)] in THF at room temperature gave the b-diketiminate lanthanide dichloride LYbCl2(THF)2 (1) in good isolated yield. Similarly reac...Reaction of anhydrous YbCl3 with 1 equiv. of LLi [L=p-ClPhNC(Me)CH(Me)N(C6H3-2,6-i-Pr2)] in THF at room temperature gave the b-diketiminate lanthanide dichloride LYbCl2(THF)2 (1) in good isolated yield. Similarly reaction of anhydrous YbCl3 with 1 equiv. of LLi, then with 1 equiv. of t-BuCpNa in THF yielded the expected mixed-ligand b-diketiminate ytterbium chloride (t-BuCp)YbL(m-Cl)2Li(THF)2 (2). Both 1 and 2 were well charac-terized by elemental analysis, IR spectra, 1H NMR spectra, and X-ray diffraction analysis.展开更多
A series of lanthanide complexes.K17 [Ln (As2W17O61)2].rH2O (Ln=La, Pr,Nd, Sm, Eu,.Gd or Dy) have been prepared and characterized by elemental analysis,IR.183W NMR and electrochemistry.
Utilizing two polycarboxylic acids as primary ligands and 1,10-phenanthrolion as an auxiliary ligand in the existence of lanthanide nitrates, two lanthanide-based complexes formulated as [Nd4（2,6-pydc OH）6（Phen）4...Utilizing two polycarboxylic acids as primary ligands and 1,10-phenanthrolion as an auxiliary ligand in the existence of lanthanide nitrates, two lanthanide-based complexes formulated as [Nd4（2,6-pydc OH）6（Phen）4（H2O）2]（H2O）2（1） and [Yb2（mBDC）3（Phen）2]n（2）（2,6-H2 pydc OH = 4-hydroxypyridine-2,6-dicarboxylic acid, m-H_2BDC = isophthalic acid, Phen = 1,10-phenanthroline） have been solvothermally synthesized. They have been fully characterized by satisfactory elemental analysis, FT-IR spectra, TGA and single-crystal X-ray diffraction. Single-crystal X-ray diffraction study reveals that 1 has a zero-dimensional structure and 2 exhibits a rare cds topological net structure. Compounds 1 and 2 exhibit strong characteristic emissions of Nd（Ⅲ） and Yb（Ⅲ） ions in the near-infrared（NIR） region.展开更多
The complexes of cyclopentadienyl tetramethylethenebridsied dicyclopentadienylsamarium (Ⅲ) tetrahydrofuranates, Me4C2(C5H4)2LnC5H5 (THF) (Ln = Nd, Sm, Gd, Yb) were synthesized and characterized by elemental analysis,...The complexes of cyclopentadienyl tetramethylethenebridsied dicyclopentadienylsamarium (Ⅲ) tetrahydrofuranates, Me4C2(C5H4)2LnC5H5 (THF) (Ln = Nd, Sm, Gd, Yb) were synthesized and characterized by elemental analysis, IR, 1HNMR, thermogravimetry and MS. The crystal structure of Me4C2(C5H4)2SmC5H5 was determined by X-ray diffraction method. The crystal belongs orthorhombic space group Cc2a. with a =1 . 1696(6) nm, b =1 .2539(5) nm, c = 2.9432(15) nm, V= 4.316 (4) nm3, Z= 8 and Dc = 1 . 54 g . cm-3.展开更多
文摘The reaction of MeCpLnCl·2LiCl·nTHF with 2 equivalent of LiNPh_2 in THF,hexane and toluene mixture solution gives the new complex[Li(DME)_2][(η~5-MeCp)Ln(NPh_2)_3](Ln=La,Pr,Nd)by extraction with DME.They have been characterized by elemental analysis,IR and NMR.The La complex crystallizes in the monoclinic space group P2_1/c with α=1.8335(6)nm,b=1.6576(5)nm,c=1.7461(6)nm, β=96.04°,V=5.277 nm^2,Z=4,D_c=1.26g·cm^(-3),R=0.057 and R_w=0.048(1≥2.5σ(I_o))for 3378 reflec- tions.The complex consists of a pair of a cation and an anion.La^(3+) is coordinated by one methylcyclopentadienyl and three diphenylamidos to form six-coordinate pseudotetrahedron with the mean Ln-N and La-C(ring)distances of 0.2459(8)and 0.2843(11)nm,respectively.
文摘The lanthanide Schiff base complex [2-OC6H4CHN(2,6-i-Pr2C6H3)]2ErCl(THF) (C42H52ClErN2O3) has been prepared by the reaction of anhydrous LnCl3 with 2 equiv. of the sodium salt of the bidentate Schiff base N-(2,6-diisopropylphenyl)salicylaldimine in THF. The crystal structure was determined by X-ray diffraction analysis. The crystal belongs to triclinic, space group P1 with a = 9.200(1), b = 13.637(2), c = 16.705(2) ? a = 74.493(7), b = 77.979(8), g = 81.306(8), V = 1965.2(4) ?, Z = 2, Mr = 835.60, Dc = 1.412 g/cm3, F(000) = 854, T = 193 K, l(MoKa) = 0.7107 ?and m = 22.38 cm-1. The final R = 0.052 and wR = 0.076 for 8386 observed reflections with I ≥ 2s(I).
基金the National Natural Science Foundation of Chinathe Natural Science Foundation of Jiangsu Province (BK2007505)Major Basic Research Project of the Natural Science Foundation of the Jiangsu Higher Education Institutions (07KJA15014)
文摘The lanthanide complexes containing a bulky tridentate [N,N,O] Schiff base ligand 3,5-But2-2-（OH）C6H2CH=N-8-C9H6N （HL） were synthesized and characterized. The reaction of anhydrous LnCl3 with NaL formed in situ in a 1：1 molar ratio in THF at room temperature afforded the lanthanide Schiff base dichloride complexes LnLCl2（DME） （Ln=Eu （1）; Sm （2））. Complexes 1 and 2 can be used as precursors for the synthesis of the lanthanide cyclopentadienyl Schiff base derivatives. The reactions of complexes 1 and 2 with one equiv of NaCH3C5H4 in THF provided the desired products LnL（CH3C5H4）CI（THF）.THF （Ln=Eu （3）; Sm （4）） in good isolated yields. These complexes were characterized by elemental analysis, IR spectra, and X-ray structural determination, in the case of complexes 3 and 4. The crystal data of complex 3 are monoclinic, P21/C space group, a=1.3370（2） nm, b=1.5190（2） nm, c=1.8910（3） nm, β=109.846（4）°, V=3.6125（8） nm^3, Z=4, Dc=1.416 mg/m^3,μ=1.847 mm^-1, F（000）=1584, R=0.0707, wR=0.1350. The crystal data of complex 4 are monoclinic, P21/c space group, a=1.3383（1） nm, b=1.5210（2） nm, c=1.8960（2） nm, β =109.878（3）°, V=3.6293（7） nm^3, Z=4, Dc=1.407 mg/m^3, μ=1.728 mm^-1, F（000）= 1580, R=0.0670, wR=0.1385.
基金ProjectsupportedbytheMajorStateBasicResearchDevelopmentProgram (No .G19990 64 80 1) .
文摘Reaction of anhydrous ytterbium trichlorides with 2 equiv. of cyclopentylindenyl lithium in THF solution, followed by removal of the solvent and crystallization of the product from diethyl ether, affords a crystal complex of the composition (C 5H 9C 9H 6) 2Yb( μ Cl) 2Li(Et 2O) 2. Crystallographic analysis shows that the ytterbium coordinated by two cyclopentylindenyl rings and lithium surrounded by two ether molecules are bridged by the two chlorine atoms and Yb, Li and two chlorine atoms form a plane.
基金theNationalNaturalScienceFoundationofChina (No .2 0 0 72 0 2 7)
文摘Two new 15-membered functionalized macrocycles, dioxo^polyazacycloalkanes with three pendant acetato groups, have been synthesized by the condensation reaction of DTPA dianhydride (DTPA=diethylenetriaminepentaacetic acid) with 1,2-diaminopropane, (15-DTPA-1,2-pn), or 1,2-diaminocyclohexane, (15-DTPA-1,2-cy). Their lanthanide complexes [Ln(15-DTPA-1,2-pn)(H 2O)] 2 [Ln=Eu (1), Gd (2)] and [Ln(15-DTPA-1,2-cy)(H 2O)] 2 [Ln=Eu (3), Gd (4)] were also prepared. Single crystal X-ray diffraction analyses of complexes 2 and 4 show that they have dimeric structures in solid state; each metal ion is nine-coordinated in a distorted tricapped-trigonal prism. In complex 4, the coexistence of two diastereoisomeric molecules in the crystal lattice was observed.
基金theNationalNaturalScienceFoundationofChina (No .2 0 0 72 0 2 7)
文摘Anhydrous LnCl 3 reacts with 2 equiv. of the sodium salt of the bidentate Schiff base N (2,6 diisopropylphenyl)salicylaldimine in THF to form the monomeric lanthanide chlorides [2 OC 6H 4CH= N(2,6 i Pr 2C 6H 3) ] 2LnCl(THF) [Ln=Yb (1), Er (2)]. Complex 1 crystallizes in P 1 space group with a =0 9215(2) nm, b = 1 36612(4) nm, c =1 6899(2) nm, α =74 83(3)°, β = 77 43(2)°, γ =81 04(1)°, Z =2, V =1 9929(4) nm 3, D c=1 402 g/cm 3. The two complexes exhibited fairly good catalytic activity in the ring opening polymerization of ε caprolactone.
基金Project supported by the National Natural Science Foundation of China (No. 20272040) and Ningbo Science and Technology Bureau.
文摘Reaction of anhydrous YbCl3 with 1 equiv. of LLi [L=p-ClPhNC(Me)CH(Me)N(C6H3-2,6-i-Pr2)] in THF at room temperature gave the b-diketiminate lanthanide dichloride LYbCl2(THF)2 (1) in good isolated yield. Similarly reaction of anhydrous YbCl3 with 1 equiv. of LLi, then with 1 equiv. of t-BuCpNa in THF yielded the expected mixed-ligand b-diketiminate ytterbium chloride (t-BuCp)YbL(m-Cl)2Li(THF)2 (2). Both 1 and 2 were well charac-terized by elemental analysis, IR spectra, 1H NMR spectra, and X-ray diffraction analysis.
文摘A series of lanthanide complexes.K17 [Ln (As2W17O61)2].rH2O (Ln=La, Pr,Nd, Sm, Eu,.Gd or Dy) have been prepared and characterized by elemental analysis,IR.183W NMR and electrochemistry.
基金supported by the National Basic Research Program of China(973 Program,2012CB821702)the National Natural Science Foundation of China(21233009 and 21571175)the State Key Laboratory of Structural Chemistry
文摘Utilizing two polycarboxylic acids as primary ligands and 1,10-phenanthrolion as an auxiliary ligand in the existence of lanthanide nitrates, two lanthanide-based complexes formulated as [Nd4（2,6-pydc OH）6（Phen）4（H2O）2]（H2O）2（1） and [Yb2（mBDC）3（Phen）2]n（2）（2,6-H2 pydc OH = 4-hydroxypyridine-2,6-dicarboxylic acid, m-H_2BDC = isophthalic acid, Phen = 1,10-phenanthroline） have been solvothermally synthesized. They have been fully characterized by satisfactory elemental analysis, FT-IR spectra, TGA and single-crystal X-ray diffraction. Single-crystal X-ray diffraction study reveals that 1 has a zero-dimensional structure and 2 exhibits a rare cds topological net structure. Compounds 1 and 2 exhibit strong characteristic emissions of Nd（Ⅲ） and Yb（Ⅲ） ions in the near-infrared（NIR） region.
文摘The complexes of cyclopentadienyl tetramethylethenebridsied dicyclopentadienylsamarium (Ⅲ) tetrahydrofuranates, Me4C2(C5H4)2LnC5H5 (THF) (Ln = Nd, Sm, Gd, Yb) were synthesized and characterized by elemental analysis, IR, 1HNMR, thermogravimetry and MS. The crystal structure of Me4C2(C5H4)2SmC5H5 was determined by X-ray diffraction method. The crystal belongs orthorhombic space group Cc2a. with a =1 . 1696(6) nm, b =1 .2539(5) nm, c = 2.9432(15) nm, V= 4.316 (4) nm3, Z= 8 and Dc = 1 . 54 g . cm-3.
