3,5-Dimethylpyrazole (HPzMe2) reacted with (C5H5)3Y in THF to yield dinuclear complexes [(C5H5)Y-(η2-PzMe2)(μ-PzMe2)]2 ( I ) and [Y(η2-PzMe2)2(μ-PzMe2)-(μ-THF)]2 (II), revealing a new method for synthesizing tris...3,5-Dimethylpyrazole (HPzMe2) reacted with (C5H5)3Y in THF to yield dinuclear complexes [(C5H5)Y-(η2-PzMe2)(μ-PzMe2)]2 ( I ) and [Y(η2-PzMe2)2(μ-PzMe2)-(μ-THF)]2 (II), revealing a new method for synthesizing tris(pyrazolate) complexes of lanthanide metals. The X-ray crystallographic analysis showed that complex II crystallizes in space group P 1 , with unit cell dimensions a = 1.0798(1), b = 1.0818(1), c = 1.1313(1) nm, a = 76.914(2)°,(B = 68.940(2)°, γ= 60.510(2)°, V = 1.0715(2) nm3, Z = 1. The final R factor is 0.0445. The investigation results showed that Me2SiO can only be inserted into the Y-N (bridging) bond of complex I to form [(C5H5)Y(η2-PzMe2)(μ-OSiMe2 PzMe2)]2 (Ⅲ), but cannot be inserted into the Y-N (bridging) bond of complex II due to the bulky crowding of the tetraple bridge structure.展开更多
C l2M eS iS iM eC l2与环戊二烯基锂及对甲苯基溴化镁反应,生成C5H5(p-Tol)M eS iS iM e(p-Tol)C5H5.后者再与五羰基铁反应,得到标题化合物[η5,η5-C5H4(p-Tol)M eS iS iM e(p-Tol)C5H4]Fe2(CO)2(μ-CO)2(3);同时还得到两个单硅桥连...C l2M eS iS iM eC l2与环戊二烯基锂及对甲苯基溴化镁反应,生成C5H5(p-Tol)M eS iS iM e(p-Tol)C5H5.后者再与五羰基铁反应,得到标题化合物[η5,η5-C5H4(p-Tol)M eS iS iM e(p-Tol)C5H4]Fe2(CO)2(μ-CO)2(3);同时还得到两个单硅桥连副产物[η5,η5-(p-Tol)2M eS iS iM e(C5H4)2]Fe2(CO)2(μ-CO)2(4)和[η5,η5-(p-Tol)M e2S iS iM e(C5H4)2]Fe2(CO)2(μ-CO)2(5).化合物3中顺式异构体(3a)占绝对优势,可通过简单重结晶分离出纯品.化合物3a在加热条件下发生分子内的硅硅键和铁铁键之间的复分解重排反应,生成[η5-(p-Tol)M eS iC5H4Fe(CO)2]2(6).该产物为顺反异构体的混合物(顺反异构体的摩尔比为4∶3),表明重排反应不涉及协同历程.利用X射线衍射法测定了化合物4的分子结构.展开更多
Treatment of Cp3Y with EtSH, followed by reaction with an equivalent of PhNCO, yielded the dinuclear complex [Cp2Y（μ-η^1：η^3-OC（SEt）NPh）]2. The structure was characterized by elemental analysis, IR, MS and sin...Treatment of Cp3Y with EtSH, followed by reaction with an equivalent of PhNCO, yielded the dinuclear complex [Cp2Y（μ-η^1：η^3-OC（SEt）NPh）]2. The structure was characterized by elemental analysis, IR, MS and single-crystal X-ray diffraction analysis. The title compound crystallizes in triclinic, space group P1^- with a = 8.643（3）, b = 10.752（4）, c = 11.161（4）A°, α= 117.840（5）, β = 94.086（5）, γ= 101.008（5）°, V = 884.8（6） A°^3, Z = 1, Mr = 798.66 （C38H40N2O2S2Y2）, λ（MoKα） = 0.710730 .A°, ,μ= 3.417 mm^-1, Dc = 1.499 g/cm^3, F（000） = 408, the final R = 0.0453 and wR = 0.1007 for 3067 unique reflections （Rint = 0.0317） with 2357 observed ones （I 〉 2σ（I））. X-ray analysis reveals an unusual bonding mode of the OC（SEt）NPh ligand and the OCN fragment acts as a both bridging and side-on chelating ligand. Each yttrium atom is coordinated by two η^5-cyclopentadienyl groups, one chelating η^3-OC（SEt）NPh ligand and one bridging O atom from another η^3-OC（SEt）NPh ligand.展开更多
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
The mixed tris-cyclopentadienyl tetrahydrofuranato samarium complexes bis-(cyclopentadienyl) methylcyclopentadienyl tetrahadrofuranato samarium (Ⅰ) was synthesized by reaction of (C_5H_5)_2SmCl with methyl cyclopenta...The mixed tris-cyclopentadienyl tetrahydrofuranato samarium complexes bis-(cyclopentadienyl) methylcyclopentadienyl tetrahadrofuranato samarium (Ⅰ) was synthesized by reaction of (C_5H_5)_2SmCl with methyl cyclopentadienyl sodium in THF. [(C_5H_5)_2(C_5H_4CH_3)(C_4H_8O)Sm] (Ⅰ) was characterized by elemental analyses, IR spectra and MS spectra. The structure of [(C_5H_5)_2(C_5H_4CH_3)(C_4H_8O)Sm] (Ⅰ), which has two slightly different independent molecules per asymmetric unit, was elucidated through complete X-ray analysis. The crystals are monoclinic with a=1.2791(3) nm, (b=1.0467(2) nm,) c=2.6108(5) nm, β=98.22(2)°, space group Cc, R=0.0381 for 2103 observed reflection with I3σ(I).展开更多
Three new chiral binuclear organolanthanide alkoxides containing cyclopentadienyl ligand have been synthesised by the reaction of Cp3Ln (Cp=C5H5; Ln=Yb, Y, Dy ) with 0.5equimolar chiral diol in THF (tetrahydrofuran) a...Three new chiral binuclear organolanthanide alkoxides containing cyclopentadienyl ligand have been synthesised by the reaction of Cp3Ln (Cp=C5H5; Ln=Yb, Y, Dy ) with 0.5equimolar chiral diol in THF (tetrahydrofuran) at -78℃ at room temperature. All the complexes were characterized by elemental analysis, IR and MS spectra.展开更多
Two new complexes [η^5-C5H4CMe2-（p-fluorophenyl）]TiCL3 （1） and [η^5-C4h4C（cyclo-C5H10）-（p-fluorophenyl）]TiCl3 （2） were synthesized and characterized. Their activities and selectivities for trimerization of...Two new complexes [η^5-C5H4CMe2-（p-fluorophenyl）]TiCL3 （1） and [η^5-C4h4C（cyclo-C5H10）-（p-fluorophenyl）]TiCl3 （2） were synthesized and characterized. Their activities and selectivities for trimerization of ethylene were investigated. The introduction of fluorine atom greatly weakened the arene coordination, but this disadvantageous factor can be eliminated by introduction of a bulky substituent, such as cyclo-C5H10, to the bridging carbon linked to the Cp ring. The combinative effect of the fluorine substitute and the bridging unit can make complex 2 as a highly active and selective catalyst for ethylene trimerization. Its productivity and selectivity for 1-hexene can reach 1024.0 kg·mol^-1·h^-1 and 99.3% respectively.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
[Cp2Ln（μ-SR）]2 was reacted with Ph2C=C=O to yield ketene mono-insertion products [Cp2Ln（μ-η1：η2-OC（SR）=CPh2）]2 [R=Bn, Ln=Yb （1）, Er （2）, Y （3） and R--Ph, Ln=Yb （4）], indicating that the reactions of...[Cp2Ln（μ-SR）]2 was reacted with Ph2C=C=O to yield ketene mono-insertion products [Cp2Ln（μ-η1：η2-OC（SR）=CPh2）]2 [R=Bn, Ln=Yb （1）, Er （2）, Y （3） and R--Ph, Ln=Yb （4）], indicating that the reactions of organolanthanide thiolates with ketenes are independent of the nature of the thiolate ligand and the ketene as well as the reaction condition. These reactions could provide an efficient method for the synthesis of organolanthanide complexes with the a-thiolate-substituted enolate ligand. All these complexes were characterized by elemental analysis and spectroscopic properties and the structure of complex 1 was determined through X-ray single crystal diffraction analysis.展开更多
The reactions of the mixture of 1- and 2-[2,2-bis（3,5-dimethylpyrazol-l-yl）-1-phenylethyl]-1,3-cyclopentadiene （bpzpcpH） and mixture of 1- and 2-[2,2-bis（3,5-dimethylpyrazol-l-yl）-I,l-diphenylethyl]-l,3-cyclopen...The reactions of the mixture of 1- and 2-[2,2-bis（3,5-dimethylpyrazol-l-yl）-1-phenylethyl]-1,3-cyclopentadiene （bpzpcpH） and mixture of 1- and 2-[2,2-bis（3,5-dimethylpyrazol-l-yl）-I,l-diphenylethyl]-l,3-cyclopentadiene （bpzdpcpH） with W（CO）sTHF have been carried out. The former yields complex （bpzpcpH）W（CO）4, in which the bpzpcpH acts as a k2-（N,N） bidentate ligand, and the cyclopentadiene moiety does not participate in the coordination to the tungsten atom. While the latter gives complex （bpzdpcpH）W（CO）3, in which the cyclopentadiene moiety coordinates to the tungsten atom in η2-fashion instead of general η5-coordinated mode, causing bpzdpcpH to act as a tridentate k3-（π,N,N） ligand,展开更多
A series of new complexes, CpTiCl[S2P(OR)2]2 (where R) Et, n-Pr, i-Pr, Bui, Ph) and CpTiCl [S2POGO]2 (where G) –CH2CMe2CH2-, -CMe2CMe2-) have been prepared by the drop wise addition of the appropriate O, O’-dialkyl ...A series of new complexes, CpTiCl[S2P(OR)2]2 (where R) Et, n-Pr, i-Pr, Bui, Ph) and CpTiCl [S2POGO]2 (where G) –CH2CMe2CH2-, -CMe2CMe2-) have been prepared by the drop wise addition of the appropriate O, O’-dialkyl or -alkylene dithiophosphoric acid to cyclopentadienyl titanium trichloride in 1:2 molar ratio and refluxed in benzene solution. The new compounds were characterized by molecular weight measurements elemental analyses and spectroscopic studies (1H, 13C, and 31P NMR, and in-frared). We suggest a distorted tetrahedron structure of these new complexes and the dithioligand behaves as bidentate ligand.展开更多
The title complex {CpEu CH(COOC 2H 5) 2 μ CH(COOC 2H 5) 2 } 2 crystallizes in the triclinic system, space group P1 with unit cell constants a=9.108(1), b=11.580(2), c=11.705(2) , α=70.42(1)...The title complex {CpEu CH(COOC 2H 5) 2 μ CH(COOC 2H 5) 2 } 2 crystallizes in the triclinic system, space group P1 with unit cell constants a=9.108(1), b=11.580(2), c=11.705(2) , α=70.42(1)°, β=73.83(1)°, γ=78.60(1)°, D c =1.602 g/cm 3 , M r=1070.76, V=1109.7(3) 3, Z=1, μ (Mo Kα )=28 66 cm 1 and F(000)=536, T=296K, R=0.028, R w =0.037. The geometry around the Eu ion can be described as a pentagonal bipyramid.展开更多
基金This work was supported by the National Natural Science Foundation of China (Grant No. 29872009) the Shanghai Shu-guang Foundation and the Open Laboratory of Organometallic Chemistry, the Chinese Academy of Sciences.
文摘3,5-Dimethylpyrazole (HPzMe2) reacted with (C5H5)3Y in THF to yield dinuclear complexes [(C5H5)Y-(η2-PzMe2)(μ-PzMe2)]2 ( I ) and [Y(η2-PzMe2)2(μ-PzMe2)-(μ-THF)]2 (II), revealing a new method for synthesizing tris(pyrazolate) complexes of lanthanide metals. The X-ray crystallographic analysis showed that complex II crystallizes in space group P 1 , with unit cell dimensions a = 1.0798(1), b = 1.0818(1), c = 1.1313(1) nm, a = 76.914(2)°,(B = 68.940(2)°, γ= 60.510(2)°, V = 1.0715(2) nm3, Z = 1. The final R factor is 0.0445. The investigation results showed that Me2SiO can only be inserted into the Y-N (bridging) bond of complex I to form [(C5H5)Y(η2-PzMe2)(μ-OSiMe2 PzMe2)]2 (Ⅲ), but cannot be inserted into the Y-N (bridging) bond of complex II due to the bulky crowding of the tetraple bridge structure.
文摘C l2M eS iS iM eC l2与环戊二烯基锂及对甲苯基溴化镁反应,生成C5H5(p-Tol)M eS iS iM e(p-Tol)C5H5.后者再与五羰基铁反应,得到标题化合物[η5,η5-C5H4(p-Tol)M eS iS iM e(p-Tol)C5H4]Fe2(CO)2(μ-CO)2(3);同时还得到两个单硅桥连副产物[η5,η5-(p-Tol)2M eS iS iM e(C5H4)2]Fe2(CO)2(μ-CO)2(4)和[η5,η5-(p-Tol)M e2S iS iM e(C5H4)2]Fe2(CO)2(μ-CO)2(5).化合物3中顺式异构体(3a)占绝对优势,可通过简单重结晶分离出纯品.化合物3a在加热条件下发生分子内的硅硅键和铁铁键之间的复分解重排反应,生成[η5-(p-Tol)M eS iC5H4Fe(CO)2]2(6).该产物为顺反异构体的混合物(顺反异构体的摩尔比为4∶3),表明重排反应不涉及协同历程.利用X射线衍射法测定了化合物4的分子结构.
基金This work was supported by the National Natural Science Foundation of China (No. 20372016)
文摘Treatment of Cp3Y with EtSH, followed by reaction with an equivalent of PhNCO, yielded the dinuclear complex [Cp2Y（μ-η^1：η^3-OC（SEt）NPh）]2. The structure was characterized by elemental analysis, IR, MS and single-crystal X-ray diffraction analysis. The title compound crystallizes in triclinic, space group P1^- with a = 8.643（3）, b = 10.752（4）, c = 11.161（4）A°, α= 117.840（5）, β = 94.086（5）, γ= 101.008（5）°, V = 884.8（6） A°^3, Z = 1, Mr = 798.66 （C38H40N2O2S2Y2）, λ（MoKα） = 0.710730 .A°, ,μ= 3.417 mm^-1, Dc = 1.499 g/cm^3, F（000） = 408, the final R = 0.0453 and wR = 0.1007 for 3067 unique reflections （Rint = 0.0317） with 2357 observed ones （I 〉 2σ（I））. X-ray analysis reveals an unusual bonding mode of the OC（SEt）NPh ligand and the OCN fragment acts as a both bridging and side-on chelating ligand. Each yttrium atom is coordinated by two η^5-cyclopentadienyl groups, one chelating η^3-OC（SEt）NPh ligand and one bridging O atom from another η^3-OC（SEt）NPh ligand.
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.
文摘The mixed tris-cyclopentadienyl tetrahydrofuranato samarium complexes bis-(cyclopentadienyl) methylcyclopentadienyl tetrahadrofuranato samarium (Ⅰ) was synthesized by reaction of (C_5H_5)_2SmCl with methyl cyclopentadienyl sodium in THF. [(C_5H_5)_2(C_5H_4CH_3)(C_4H_8O)Sm] (Ⅰ) was characterized by elemental analyses, IR spectra and MS spectra. The structure of [(C_5H_5)_2(C_5H_4CH_3)(C_4H_8O)Sm] (Ⅰ), which has two slightly different independent molecules per asymmetric unit, was elucidated through complete X-ray analysis. The crystals are monoclinic with a=1.2791(3) nm, (b=1.0467(2) nm,) c=2.6108(5) nm, β=98.22(2)°, space group Cc, R=0.0381 for 2103 observed reflection with I3σ(I).
文摘Three new chiral binuclear organolanthanide alkoxides containing cyclopentadienyl ligand have been synthesised by the reaction of Cp3Ln (Cp=C5H5; Ln=Yb, Y, Dy ) with 0.5equimolar chiral diol in THF (tetrahydrofuran) at -78℃ at room temperature. All the complexes were characterized by elemental analysis, IR and MS spectra.
基金Project supported by the National Natural Science Foundation of China （No. 20372022） and the Major State Basic Research Development Program of China （No. 2005CB623801）.
文摘Two new complexes [η^5-C5H4CMe2-（p-fluorophenyl）]TiCL3 （1） and [η^5-C4h4C（cyclo-C5H10）-（p-fluorophenyl）]TiCl3 （2） were synthesized and characterized. Their activities and selectivities for trimerization of ethylene were investigated. The introduction of fluorine atom greatly weakened the arene coordination, but this disadvantageous factor can be eliminated by introduction of a bulky substituent, such as cyclo-C5H10, to the bridging carbon linked to the Cp ring. The combinative effect of the fluorine substitute and the bridging unit can make complex 2 as a highly active and selective catalyst for ethylene trimerization. Its productivity and selectivity for 1-hexene can reach 1024.0 kg·mol^-1·h^-1 and 99.3% respectively.
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.
基金Project supported by the National Natutral Science Foundation of China （No. 20372016）.
文摘[Cp2Ln（μ-SR）]2 was reacted with Ph2C=C=O to yield ketene mono-insertion products [Cp2Ln（μ-η1：η2-OC（SR）=CPh2）]2 [R=Bn, Ln=Yb （1）, Er （2）, Y （3） and R--Ph, Ln=Yb （4）], indicating that the reactions of organolanthanide thiolates with ketenes are independent of the nature of the thiolate ligand and the ketene as well as the reaction condition. These reactions could provide an efficient method for the synthesis of organolanthanide complexes with the a-thiolate-substituted enolate ligand. All these complexes were characterized by elemental analysis and spectroscopic properties and the structure of complex 1 was determined through X-ray single crystal diffraction analysis.
基金Project supported by the National Natural Science Foundation of China （No. 20672059）.
文摘The reactions of the mixture of 1- and 2-[2,2-bis（3,5-dimethylpyrazol-l-yl）-1-phenylethyl]-1,3-cyclopentadiene （bpzpcpH） and mixture of 1- and 2-[2,2-bis（3,5-dimethylpyrazol-l-yl）-I,l-diphenylethyl]-l,3-cyclopentadiene （bpzdpcpH） with W（CO）sTHF have been carried out. The former yields complex （bpzpcpH）W（CO）4, in which the bpzpcpH acts as a k2-（N,N） bidentate ligand, and the cyclopentadiene moiety does not participate in the coordination to the tungsten atom. While the latter gives complex （bpzdpcpH）W（CO）3, in which the cyclopentadiene moiety coordinates to the tungsten atom in η2-fashion instead of general η5-coordinated mode, causing bpzdpcpH to act as a tridentate k3-（π,N,N） ligand,
文摘A series of new complexes, CpTiCl[S2P(OR)2]2 (where R) Et, n-Pr, i-Pr, Bui, Ph) and CpTiCl [S2POGO]2 (where G) –CH2CMe2CH2-, -CMe2CMe2-) have been prepared by the drop wise addition of the appropriate O, O’-dialkyl or -alkylene dithiophosphoric acid to cyclopentadienyl titanium trichloride in 1:2 molar ratio and refluxed in benzene solution. The new compounds were characterized by molecular weight measurements elemental analyses and spectroscopic studies (1H, 13C, and 31P NMR, and in-frared). We suggest a distorted tetrahedron structure of these new complexes and the dithioligand behaves as bidentate ligand.
文摘The title complex {CpEu CH(COOC 2H 5) 2 μ CH(COOC 2H 5) 2 } 2 crystallizes in the triclinic system, space group P1 with unit cell constants a=9.108(1), b=11.580(2), c=11.705(2) , α=70.42(1)°, β=73.83(1)°, γ=78.60(1)°, D c =1.602 g/cm 3 , M r=1070.76, V=1109.7(3) 3, Z=1, μ (Mo Kα )=28 66 cm 1 and F(000)=536, T=296K, R=0.028, R w =0.037. The geometry around the Eu ion can be described as a pentagonal bipyramid.
