The formation of ( t BuCp) 2ErOEt was discussed. Its single crystal structure was determined by X ray diffraction. The crystal is monoclinic, P 2(1)/ c space group, a =1.0191(2), b =1.6203(5), c ...The formation of ( t BuCp) 2ErOEt was discussed. Its single crystal structure was determined by X ray diffraction. The crystal is monoclinic, P 2(1)/ c space group, a =1.0191(2), b =1.6203(5), c =1.2118(3) nm, β =102.960(10)°, V =1.9500 (nm 3), Z =2, D c=1.566 mg·m -3 , R =0.0450, R w=0.1363. The complex is monomeric and solvent free in the solid state. The erbium ion is coordinated by two tert butyl cyclopentadienyl rings and one oxygen atom of ethoxy group to form a seven coordinated complex.展开更多
Reactions of samarium triiodides with 2 equivalents of potassium 2-methoxyethyl- cyelopentadienyl or 1 equivalent of potassium 2-methoxyethylcyclopentadienyl in tetrehydrofuran afford bis- (2-methoxyethylcyclopentadie...Reactions of samarium triiodides with 2 equivalents of potassium 2-methoxyethyl- cyelopentadienyl or 1 equivalent of potassium 2-methoxyethylcyclopentadienyl in tetrehydrofuran afford bis- (2-methoxyethylcyclopentadienyl) samarium iodide complex Cp′_2 SmI 1 (Cp′=MeOCH_2CH_2C_5H_4),and (2- methoxyethylcyclopentadienyl) samarium diioidide complex Cp′SmI_2·2THF 2.Compound 1 crystallizes from THF/hexane in orthorhombic space group P2_12_12_1 with cell dimensions a= 11.074(4),b= 12.929(9), c=12.269(4) ,V=1756.9 ~3 and D_(cacld)=1.978 g/cm^3 for Z=4.The central metal Sm is coordinated with two Cp′ ring centroids,one iodine atom and two oxygen atoms of Cp′ forming a distorted trigonal bipyramid.The coordination number of Sm (Ⅲ) in 1 is 9.The crysal of 2 belongs to the monoclinie crystal system,space group P2_1/c with a=16.304(6),b=8.335(2),c=16.527(5) ,β=111.8 (1)°,V= 2085.3 ~3 D_(cacld)=2.138 g/cm^3 and Z=4.The central metal Sm is coordinated by one Cp′ ring centroid, two iodine atoms,one oxygen atom of Cp′ and two oxygen atoms of THF forming a distorted octahedron. The coordination number of Sm (Ⅲ) in 2 is 8.展开更多
The reaction of the THF solution of （C5H5）2NdCl· 2LiCl with n-butyllithium was studied and the neodymium hydride complex, [ Li （ DME ）3 ] [ （C5H5）3Nd （μ-H） Nd （ C5H5 ）3 ] 1 was isolated from the reacti...The reaction of the THF solution of （C5H5）2NdCl· 2LiCl with n-butyllithium was studied and the neodymium hydride complex, [ Li （ DME ）3 ] [ （C5H5）3Nd （μ-H） Nd （ C5H5 ）3 ] 1 was isolated from the reaction solution. Complex 1 was crystallized from a mixture solvent of THF-DME and structurally characterized by single crystal X-ray diffraction method at - 80 ℃. The crystal is monoclinic, space group P21/c with unit cell dimensions a = 0.9670（2） nm, b =2.1001（5） nm, c=2.1279（7） nm, β=9.089（2）°, Z = 4. The structure was solved by heavy atom method and refined by the least-squares method to a final R = 0.094. The complex consists of disconnected ion pairs of [ Li （ DME ）3 ]^＋ and [ （ C5H5 ）3Nd （μ-H） Nd （C5H5）3]^-. The neodymium atom is coordinated by three η5-cyclopentadienyls, and two （C5H5）3Nd species are connected by one hydrogen bridge to form the anion with Nd-H 0.218（1） nm.展开更多
C_6H_5CH_2C_5H_4ErCl_2(THF)_3]·THF, Mr=681.9, monoclinic,space group P2_1/n, with a=11. 622(5), b=10. 281(4), c=26. 040(5),β=86. 65 (4)°,V=3106 (3), Z=4, Dc=1. 46 gcm￣(-3),μ=30. 0 cm￣(-1), F (000)=1380. ...C_6H_5CH_2C_5H_4ErCl_2(THF)_3]·THF, Mr=681.9, monoclinic,space group P2_1/n, with a=11. 622(5), b=10. 281(4), c=26. 040(5),β=86. 65 (4)°,V=3106 (3), Z=4, Dc=1. 46 gcm￣(-3),μ=30. 0 cm￣(-1), F (000)=1380. The final R value is 0. 040 for 1911 independent observed reflections (I>3σ(I)). The geometry around the erbium ion is described as an approximate octahedron with the centroid of the benzylcyclopentadienyl rings, the oxygens of three THF's and two chlorine atoms forming the apices of the octahedron. The average distance of Er-C(Cp'ring) is 2. 66A.展开更多
Six new ethylthioethylcyclopentadienyl-containing organolanthanide complexes CpTh 2LnCl [Ln=Gd (1), Dy (2)] and Cp2LnCpTh [Cp=C5H5, Ln=Yb (3), Sm (4), Dy (5), Y (6)] were synthesized by the reaction of ethylthioethyl-...Six new ethylthioethylcyclopentadienyl-containing organolanthanide complexes CpTh 2LnCl [Ln=Gd (1), Dy (2)] and Cp2LnCpTh [Cp=C5H5, Ln=Yb (3), Sm (4), Dy (5), Y (6)] were synthesized by the reaction of ethylthioethyl-cyclopentadienyl (CpTh) sodium salt with LnCl3 or Cp2LnCl in THF. Complexes 16 were characterized by ele-mental analyses, infrared and mass spectroscopies. The molecular structures of complexes 13 were also deter-mined by the X-ray single crystal diffraction. The results show that the side-chain sulfur atom on the ethylthio-ethylcyclopentadienyl ring can form intramolecular chelating coordination to the central lanthanide ion, improving the stability of organolanthanide complexes and reducing the number of coordinated THF molecules.展开更多
Bis （methylcyclopentadienyl） lanthanide amido complex （MeCp） 2YbNPh2 （THF） reacted with n-hexyl isocyanate （n-nexylNCO） in 1：1 molar ratio to give {（MeC5H4）2Yb[OC（NPh2）N（n-hexyl）] }2（1）. Complex 1 was...Bis （methylcyclopentadienyl） lanthanide amido complex （MeCp） 2YbNPh2 （THF） reacted with n-hexyl isocyanate （n-nexylNCO） in 1：1 molar ratio to give {（MeC5H4）2Yb[OC（NPh2）N（n-hexyl）] }2（1）. Complex 1 was characterized by elemental analyses and X-ray diffraction. The title complex belongs to trigonal system and R-3 space group. Its unit cell parameters are a =2.9533（11） nm, b =2.9533（11） nm, c = 1.5873（6） nm, V= 11.9896（80） nm^3, Z =9, Dc= 1.562 mg·m^-3, μ = 3.536 mm^-1（Mo Kα）, F（000） =5670, R =0.034, Rw =0.064. It is a dimeric structure with two symmetrical bridged oxygen atoms. Nitrogen atom is coordinated to the ytterbium atom to form a tricyclic backbone. The coordination number of ytterbium is 9. The whole molecule shows central symmetry.展开更多
The crystal structure of title complex has been determined by the method of X-ray single crystal diffraction.The crystal belongs to monoclinic space group C_(2/c)with the unit parameters a=2.8907(7), b=2.0431(5),c=1.5...The crystal structure of title complex has been determined by the method of X-ray single crystal diffraction.The crystal belongs to monoclinic space group C_(2/c)with the unit parameters a=2.8907(7), b=2.0431(5),c=1.5723(3)nm;β=115.67(2)°.The unit volume V is 8.36924(348)nm^3;Z=8, Dc=1,82g·cm^(-3),μ(MoK_α)=46.4cn^(-1); F(000)=4416.The final R is 0.083,Rw 0.088.The title complex con- sists of two univalent cations and one divalent anion.The anion has a cluster structure including six Sm^(3+). Coordination numbers of all six Sm^(3+)are eight,but their surroundings are different from each other.Two of them are decahedral array,and the others are octahedral array f the centroid of each pentacyclodienyl ring is taken as one point.展开更多
经过三步反应合成了红色晶体,双六甲基二硅胺基二甲基硅基环戊二烯基稀土二价镱配合物[η5-C5H4S iM e2N(S iM e3)2]2Yb(Ⅱ).2THF,X射线衍射结果表明,[η5-C5H4S iM e2N(S iM e3)2]2Yb(Ⅱ).2THF属于单斜晶系,空间群为P21/c,a=1.646 87(1...经过三步反应合成了红色晶体,双六甲基二硅胺基二甲基硅基环戊二烯基稀土二价镱配合物[η5-C5H4S iM e2N(S iM e3)2]2Yb(Ⅱ).2THF,X射线衍射结果表明,[η5-C5H4S iM e2N(S iM e3)2]2Yb(Ⅱ).2THF属于单斜晶系,空间群为P21/c,a=1.646 87(12)nm,b=0.907 70(6)nm,c=3.049 4(3)nm,β=93.642(4),°V=4.549 3(6)nm3,Z=2,C34H72N2O2S i6Yb,Mr=1 905.41,Dc=1.288 g/cm3,F(000)=1 840.00,μ(MoKα)=22.42 cm-1(λ=0.071 070 nm)。收集独立衍射点7 814个,将其中I>3.00σ(1)的用于结构解析,用全矩阵最小二乘法校正,得最终偏离因子R=0.039,Rw=0.050。8配位的中心镱原子与2个四氢呋喃的氧及2个环戊二烯基配位形成扭曲的四面体结构。展开更多
文摘The formation of ( t BuCp) 2ErOEt was discussed. Its single crystal structure was determined by X ray diffraction. The crystal is monoclinic, P 2(1)/ c space group, a =1.0191(2), b =1.6203(5), c =1.2118(3) nm, β =102.960(10)°, V =1.9500 (nm 3), Z =2, D c=1.566 mg·m -3 , R =0.0450, R w=0.1363. The complex is monomeric and solvent free in the solid state. The erbium ion is coordinated by two tert butyl cyclopentadienyl rings and one oxygen atom of ethoxy group to form a seven coordinated complex.
基金the National Natural Science Foundation of China
文摘Reactions of samarium triiodides with 2 equivalents of potassium 2-methoxyethyl- cyelopentadienyl or 1 equivalent of potassium 2-methoxyethylcyclopentadienyl in tetrehydrofuran afford bis- (2-methoxyethylcyclopentadienyl) samarium iodide complex Cp′_2 SmI 1 (Cp′=MeOCH_2CH_2C_5H_4),and (2- methoxyethylcyclopentadienyl) samarium diioidide complex Cp′SmI_2·2THF 2.Compound 1 crystallizes from THF/hexane in orthorhombic space group P2_12_12_1 with cell dimensions a= 11.074(4),b= 12.929(9), c=12.269(4) ,V=1756.9 ~3 and D_(cacld)=1.978 g/cm^3 for Z=4.The central metal Sm is coordinated with two Cp′ ring centroids,one iodine atom and two oxygen atoms of Cp′ forming a distorted trigonal bipyramid.The coordination number of Sm (Ⅲ) in 1 is 9.The crysal of 2 belongs to the monoclinie crystal system,space group P2_1/c with a=16.304(6),b=8.335(2),c=16.527(5) ,β=111.8 (1)°,V= 2085.3 ~3 D_(cacld)=2.138 g/cm^3 and Z=4.The central metal Sm is coordinated by one Cp′ ring centroid, two iodine atoms,one oxygen atom of Cp′ and two oxygen atoms of THF forming a distorted octahedron. The coordination number of Sm (Ⅲ) in 2 is 8.
文摘The reaction of the THF solution of （C5H5）2NdCl· 2LiCl with n-butyllithium was studied and the neodymium hydride complex, [ Li （ DME ）3 ] [ （C5H5）3Nd （μ-H） Nd （ C5H5 ）3 ] 1 was isolated from the reaction solution. Complex 1 was crystallized from a mixture solvent of THF-DME and structurally characterized by single crystal X-ray diffraction method at - 80 ℃. The crystal is monoclinic, space group P21/c with unit cell dimensions a = 0.9670（2） nm, b =2.1001（5） nm, c=2.1279（7） nm, β=9.089（2）°, Z = 4. The structure was solved by heavy atom method and refined by the least-squares method to a final R = 0.094. The complex consists of disconnected ion pairs of [ Li （ DME ）3 ]^＋ and [ （ C5H5 ）3Nd （μ-H） Nd （C5H5）3]^-. The neodymium atom is coordinated by three η5-cyclopentadienyls, and two （C5H5）3Nd species are connected by one hydrogen bridge to form the anion with Nd-H 0.218（1） nm.
文摘C_6H_5CH_2C_5H_4ErCl_2(THF)_3]·THF, Mr=681.9, monoclinic,space group P2_1/n, with a=11. 622(5), b=10. 281(4), c=26. 040(5),β=86. 65 (4)°,V=3106 (3), Z=4, Dc=1. 46 gcm￣(-3),μ=30. 0 cm￣(-1), F (000)=1380. The final R value is 0. 040 for 1911 independent observed reflections (I>3σ(I)). The geometry around the erbium ion is described as an approximate octahedron with the centroid of the benzylcyclopentadienyl rings, the oxygens of three THF's and two chlorine atoms forming the apices of the octahedron. The average distance of Er-C(Cp'ring) is 2. 66A.
基金the National Natural Science Foundation of China and the Research Funds of Excellent Young Teacher and the New Century Distinguished Scientist of National Education Ministry of China.
文摘Six new ethylthioethylcyclopentadienyl-containing organolanthanide complexes CpTh 2LnCl [Ln=Gd (1), Dy (2)] and Cp2LnCpTh [Cp=C5H5, Ln=Yb (3), Sm (4), Dy (5), Y (6)] were synthesized by the reaction of ethylthioethyl-cyclopentadienyl (CpTh) sodium salt with LnCl3 or Cp2LnCl in THF. Complexes 16 were characterized by ele-mental analyses, infrared and mass spectroscopies. The molecular structures of complexes 13 were also deter-mined by the X-ray single crystal diffraction. The results show that the side-chain sulfur atom on the ethylthio-ethylcyclopentadienyl ring can form intramolecular chelating coordination to the central lanthanide ion, improving the stability of organolanthanide complexes and reducing the number of coordinated THF molecules.
文摘Bis （methylcyclopentadienyl） lanthanide amido complex （MeCp） 2YbNPh2 （THF） reacted with n-hexyl isocyanate （n-nexylNCO） in 1：1 molar ratio to give {（MeC5H4）2Yb[OC（NPh2）N（n-hexyl）] }2（1）. Complex 1 was characterized by elemental analyses and X-ray diffraction. The title complex belongs to trigonal system and R-3 space group. Its unit cell parameters are a =2.9533（11） nm, b =2.9533（11） nm, c = 1.5873（6） nm, V= 11.9896（80） nm^3, Z =9, Dc= 1.562 mg·m^-3, μ = 3.536 mm^-1（Mo Kα）, F（000） =5670, R =0.034, Rw =0.064. It is a dimeric structure with two symmetrical bridged oxygen atoms. Nitrogen atom is coordinated to the ytterbium atom to form a tricyclic backbone. The coordination number of ytterbium is 9. The whole molecule shows central symmetry.
文摘The crystal structure of title complex has been determined by the method of X-ray single crystal diffraction.The crystal belongs to monoclinic space group C_(2/c)with the unit parameters a=2.8907(7), b=2.0431(5),c=1.5723(3)nm;β=115.67(2)°.The unit volume V is 8.36924(348)nm^3;Z=8, Dc=1,82g·cm^(-3),μ(MoK_α)=46.4cn^(-1); F(000)=4416.The final R is 0.083,Rw 0.088.The title complex con- sists of two univalent cations and one divalent anion.The anion has a cluster structure including six Sm^(3+). Coordination numbers of all six Sm^(3+)are eight,but their surroundings are different from each other.Two of them are decahedral array,and the others are octahedral array f the centroid of each pentacyclodienyl ring is taken as one point.
