Ind_(2)Y(μ-Et)_(2)AlEt_(2) and Ind_(2)LnN(i-Pr)_(2)(Ln=Y,Yb)were used as a single-component catalyst for the polymerization of acrylonitrile(AN)respectively.The regularity of polymerization of AN and stereoregularity...Ind_(2)Y(μ-Et)_(2)AlEt_(2) and Ind_(2)LnN(i-Pr)_(2)(Ln=Y,Yb)were used as a single-component catalyst for the polymerization of acrylonitrile(AN)respectively.The regularity of polymerization of AN and stereoregularity of polyacrylonitrile(PAN)were also studied in both cases.Both catalysts can produce PAN with molecular weight from 10,000 to 30,000.In addition,the catalytic activity and molecular weights were increased by the addition of PhONa.展开更多
It was first found that Ind(2)Y(mu -Et)(2)AlEt2 and Ind(2)LnN(i-Pr)(2) (Ln = Y, Yb) exhibit extremely high catalytic activity in the polymerization of methyl methacrylate. The reactions can be carried out over a quite...It was first found that Ind(2)Y(mu -Et)(2)AlEt2 and Ind(2)LnN(i-Pr)(2) (Ln = Y, Yb) exhibit extremely high catalytic activity in the polymerization of methyl methacrylate. The reactions can be carried out over a quite broad range of polymerization temperatures from -30 to 50 degreesC. PMMA with high molecular weight (7.8 x 10(-5)) and high isotacticity (94%) can be obtained by using Ind(2)Y(mu -Et)(2)AlEt2, and narrow molecular weight distribution (M-w/M-n < 1.5) can be obtained by using Ind(2)LnN(i-Pr)(2) (Ln = Y, Yb).展开更多
The synthesis of organolanthanide compounds identified as LnCp^＊（MS）2PzA, Ln = Sm, Tb, Yb （MS = methanesulfonate, Cp^＊ = pentamethylcyclopentadienyl, and PzA = pyrazinamide）, by the reaction of coordination comp...The synthesis of organolanthanide compounds identified as LnCp^＊（MS）2PzA, Ln = Sm, Tb, Yb （MS = methanesulfonate, Cp^＊ = pentamethylcyclopentadienyl, and PzA = pyrazinamide）, by the reaction of coordination compounds Ln（MS）3（PzA）4 with NaCp in THF was reported. The complexes were formulated according to elemental analyses, complexometric titration with EDTA （%Ln）, and ^1H NMR. IR spectroscopy revealed that PzA coordinates with lanthanide （Ⅲ） ions and methanesulfonate coordinates via oxygen atoms in a non-equivalent manner. In preliminary catalytic studies, these compounds were active in styrene polymerization that used MAO as a cocatalyst with an activity of 12.3 kg PS molSm^-1h^-1. Differential scanning calorimetry （DSC） of polystyrene showed that the polymer was mainly atactic.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
The reaction of [(SiMe3)2NC(NC6H11)2]Li with SmCl3 in 2:1 molar ratio in THF gave bis(N,N-cyclohexyl-N创-bis(trimethylsilyl)samarium chloride, [(SiMe3)2NC(NC6H11)2]Sm(m- Cl)2Li(THF)2 1 in 85% isolated yield as pale-ye...The reaction of [(SiMe3)2NC(NC6H11)2]Li with SmCl3 in 2:1 molar ratio in THF gave bis(N,N-cyclohexyl-N创-bis(trimethylsilyl)samarium chloride, [(SiMe3)2NC(NC6H11)2]Sm(m- Cl)2Li(THF)2 1 in 85% isolated yield as pale-yellow crystals. Complex 1 was structurally characte- rized by single-crystal X-ray diffraction analysis at 289(2) K. It crystallizes in monoclinic, space group C2/c with a = 26.886(3), b = 13.677(2), c = 19.465(3) ? b = 120.26(1), V = 6182(2) ?, Z = 4, Mr = 1105.84, Dc = 1.188 g/cm3, F(000) = 2340 and m(MoKa) = 1.150 mm-1. The structure was refined to R = 0.0378 and wR = 0.0885 for 4342 observed reflections with I > 2s(I). The coordination geometry of samarium ion can be best described as a distorted pseudooctahedron.展开更多
The title complex 1.THF has been synthesized by the reaction of [HO-4,6-di-^tBu- C6H2-2-CH2{CH（IPrNCHCHN）}]C1 with NdCl3 in a 2：1 molar ratio in THF, and characterized by single-crystal X-ray diffraction. It crysta...The title complex 1.THF has been synthesized by the reaction of [HO-4,6-di-^tBu- C6H2-2-CH2{CH（IPrNCHCHN）}]C1 with NdCl3 in a 2：1 molar ratio in THF, and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P2dc with a = 9.6501 （14）, b = 16.393（2）, c = 36.745（6） ]A, β = 97.444（4）^o, V= 5763.7（15） ]A^3, Mr= 1124.69, Z = 4, Dc= 1.296 g/cm^3, μ（MoKa） = 1.175 mm-1, F（000） = 2348, the final R = 0.0729 and wR = 0.1762 for 8735 observed reflections with 1 〉 2σ（I）. Complex 1 consists of an anion [NdC15（THF）]^2- and two cations [HO-4,6-di-tBu-C6H2-2-CH2{CH（iprNCHCHN）}]2^＋ to form a layer structure by the interconnection of anions and cations via hydrogen bonding. The central metal Nd in the anionic unit is coordinated by five C1 atoms and one oxygen atom from solvated THF molecule assuming a distorted octahedral geometry.展开更多
Anhydrous SmCl 3 reacts with two equal of Li(1,3 tBu 2C 5H 3) to give a complex (1,3 tBu 2C 5H 3) 2Sm( μ Cl) 2Li(THF) 2(C 34 H 58 Cl 2LiO 2Sm, M r =726.99), monoclinic, space group P2 1/n, a=10.615(2), b=21.037(4), c...Anhydrous SmCl 3 reacts with two equal of Li(1,3 tBu 2C 5H 3) to give a complex (1,3 tBu 2C 5H 3) 2Sm( μ Cl) 2Li(THF) 2(C 34 H 58 Cl 2LiO 2Sm, M r =726.99), monoclinic, space group P2 1/n, a=10.615(2), b=21.037(4), c=17.166(3), β=93.60(3)°, V=3825\^7(13) 3, Z=4, D c =1.262Mg/m 3, μ =1.699mm -1 and F (000)=1508, final R= 0.0387 and wR =0.0741 for 5320 observed[ I2σ(I)] reflections. The average Sm-C distance is 2\^73. Sm-Cl1 and Sm-Cl2 distances are 2\^719(2) and 2.697(2), respectively. Two 1,3 tBu 2C 5H 3 ring centroids and two μ 2 bridging chloride atoms around Sm atom form a distorted tetrahedron.展开更多
The reactivity of lanthanocene thiolates [Cp2Ln（μ-SEt）]2（Ln = Er, Y, Yb） with PhEtCCO and with PhNCO was examined. Treatment of [ Cp2Ln（μ-SEt）]2 with PhEtCCO gives the α-thiolate-substituted enolate complexes...The reactivity of lanthanocene thiolates [Cp2Ln（μ-SEt）]2（Ln = Er, Y, Yb） with PhEtCCO and with PhNCO was examined. Treatment of [ Cp2Ln（μ-SEt）]2 with PhEtCCO gives the α-thiolate-substituted enolate complexes [ Cp2Ln （μ-η^1 ：η^3-OC（SEt）CPhEt）]2（Ln = Yb, Y）, while [Cp2Ln（μ-SEt）]2 react with PhNCO to give the lanthanocene amido derivatives [Cp2Ln（OC（SEt）NPh ）]2（Ln = Er, Yb）. In both cases, the insertion reaction is independent of the stoichiometric ratio and the nature of lanthanides, demonstrating that lanthanocene thiolates are high reactive toward PhEtCCO and PhNCO under the conditions involved. All complexes are characterized by elemental analysis and spectroscopic properties, of which the structures of ytterbium enolate and erbium amido are also determined by X-ray single crystal diffraction analysis, indicating that both of them are centrosymmetric binuclear structures.展开更多
Density functional theory (DFT) calculations were carried out on the compounds Cp2Ln-guan for Ln=Y, Lu, Yb, Dy and Gd, [guan=(iPrN)2CN(iPr)2]. The results were compared with the X-ray structures that were available fr...Density functional theory (DFT) calculations were carried out on the compounds Cp2Ln-guan for Ln=Y, Lu, Yb, Dy and Gd, [guan=(iPrN)2CN(iPr)2]. The results were compared with the X-ray structures that were available from the literature; the calculations reproduced quite well the experimental structural features in these complexes exhibiting distorted tetrahedron geometry. The calculated evolution of the Ln-guan bond as a function of the cation showed that lanthanide-ligand distances increased with the increa...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
（C5H4SiMe2^tBu）2Ln^nBu reacted with 1 equiv, of elemental sulfur in toluene at ambient temperature to yield the corresponding lanthanocene thiolates [（C5H4SiMe2^tBu）2Ln（μ-S^nBu）]2 （Ln = Y （1）, Er （2））. Co...（C5H4SiMe2^tBu）2Ln^nBu reacted with 1 equiv, of elemental sulfur in toluene at ambient temperature to yield the corresponding lanthanocene thiolates [（C5H4SiMe2^tBu）2Ln（μ-S^nBu）]2 （Ln = Y （1）, Er （2））. Complexes 1 and 2 have been characterized by elemental analysis, IR, mass spectroscopy and X-ray single-crystal diffraction analysis. Both complexes are of monoclinic with space group P21/c, formula C52H94S2Si4Y2 1 （C52H94S2Si4Er2 2） Mr = 1073.57 （1230.27）, a = 8.495（2） （8.41（2））, b = 26.913（8） （26.67（7））, c = 13.756（4） （13.68（4）） A, α = 90（90）, β = 101.184（5） （101.57（4））, γ = 90 （90）°, V= 3085.1（15） （3007（14）） A^3, Dc = 1.156 （1.359） g·cm^-3, Z= 2 （2）, F（000） = 1144 （1260）, μ = 2.046 （2.951） cm^-1, R = 0.0687 （0.0749） and wR = 0.1306 （0.1507） for observed reflections with I 〉 2σ（I）. X-ray structures of 1 and 2 definitively prove that only one sulfur atom is inserted into the Ln-C（^nBu） bond, forming a thiolate ligand.展开更多
The article reviewed the progress in organolanthanide chemistry in China. The contents included the syntheses and molecular structures of organolanthanide complexes, such as tricyclopentadienyl,cyclopentadienyl halide...The article reviewed the progress in organolanthanide chemistry in China. The contents included the syntheses and molecular structures of organolanthanide complexes, such as tricyclopentadienyl,cyclopentadienyl halides, complexes containing Li-C σ bond,organohydrides, allyl-, cyclooctatetraenyl,tetraenyl-, neutral arene complexes and divalent complexes,and the application to the catalytic and organic reactions including hydrogenation,isomerization, polymerization,dehalogenation,deoxyenation and desulfuration.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
The title complex L3Y（L = [O-4,6-di-tBu-C6H2-2-CH{CH（iPr2NCHCHN） }]） has been synthesized by the reaction of LiY[N（iPr） 2]4 with H2LCl and LiBu in a 1：3：2 molar ratio at 0 ℃ in THF,and characterized by single...The title complex L3Y（L = [O-4,6-di-tBu-C6H2-2-CH{CH（iPr2NCHCHN） }]） has been synthesized by the reaction of LiY[N（iPr） 2]4 with H2LCl and LiBu in a 1：3：2 molar ratio at 0 ℃ in THF,and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic,space group P21 with a = 14.3612（16） ,b = 14.7524（14） ,c = 16.898（2） ,β = 105.708（3） o,V = 3446.3（6） A^3,Mr = 1203.50,Z = 2,Dc = 1.160 Mg/m^3,μ（MoKα） = 0.90 mm^-1 and F（000） = 1296. The structure was refined to R = 0.050 and wR = 0.110 for 10213 observed reflections with I 〉 2σ（I） . The Y ion is coordinated to three phenoxo groups and three NHC ligands to form a distorted octahedral geometry. The temperature effect on the reaction leads to the 1,2-benzyl migration of NHC ligand to form the title complex.展开更多
Reaction of DyCl 3 with excessive amount of K and indene in THF forms (C 9H 7) 3Dy(THF), which crystallizes in hexagonal system, space group P6 3 with a= b=11.719(5), c=10.167(2) , V=1211(1) 3, M r=580.0...Reaction of DyCl 3 with excessive amount of K and indene in THF forms (C 9H 7) 3Dy(THF), which crystallizes in hexagonal system, space group P6 3 with a= b=11.719(5), c=10.167(2) , V=1211(1) 3, M r=580.07, D c =1 590 g/cm 3, Z=2, F(000)=578, μ =31.31 cm -1 . Final R =0.043 and R w =0.055 for 1273 observed reflections with I>3σ(I ). The crystal structure shows that in the title compound the indenyl group is bonded to dysprosium in an η 3+η 2 fashion, and is bent over the C(1) and C(3) axis by 12.7°. Its nodal carbon atoms C(4) and C(9) which are weakly bonded to the metal atom are at distances of 2.92(1) and 2.94(1) , respectively. The average Dy-C( η 3) bond distance is 2.66(1) .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
Three homoleptic lanthanide complexes, [C6H5COCHC（CH3）N（p-CIC6H4）]3Ln（THF）n （n = 0, Ln = Yb （1）; n = 0, Ln = Y （2）; n = 1, Ln = Nd （3））, were synthesized by amine elimination reaction of Ln[N（SiMe3）2]3...Three homoleptic lanthanide complexes, [C6H5COCHC（CH3）N（p-CIC6H4）]3Ln（THF）n （n = 0, Ln = Yb （1）; n = 0, Ln = Y （2）; n = 1, Ln = Nd （3））, were synthesized by amine elimination reaction of Ln[N（SiMe3）2]3 with 1-phenyl-3-N-（p-chlorophenylimino）-1-butanone. These com- plexes crystallize in triclinic, space group PI with a = 9.805（3）, b = 14.831（6）, c = 16.075（6） A, a = 111.996（9）, β = 91.570（7）, y = 93.744（6）° V= 2159.4（13） A3, Z= 2, Dc = 1.515 g/cm3, F（000） = 986, μ（MoKa） = 2.396 mm-1, R = 0.0360 and wR = 0.0850 for 9548 observed reflections with I 〉 20（I） for complex 1; a = 9.861（5）, b = 14.852（9）, c = 16.111（9） A, a = 112.362（13）,β = 91.949（11）, y = 93.678（14）°, V= 2173（2） A3, Z= 2, Dc = 1.377 g/cm3, F（000） = 924,μ（MoKa） = 1.570 mm-1, R = 0.0735 and wR = 0.1389 for 8015 observed reflections with I 〉 20（I） for complex 2; and a = 9.308（3）, b = 15.357（3）, c = 17.419（4） A, a = 66.493（13）, β = 88.61（2）, y = 86.664（19）°, V = 2279.4（9） A3, Z= 2, Dc = 1.499 g/cm3, F（000） = 1046,μ（MoKa） = 1.364 mm-1, R = 0.0843 and wR = 0.2280 for 8433 observed reflections with I 〉 20（I） for complex 3. Each central metal in complexes 1 and 2 is six-coordinated by three nitrogen and three oxygen atoms from three β-ketoiminate ligands to give a distorted octahedral geometry, while the central metal in 3 is seven-coordinated by three nitrogen and three oxygen atoms from three β-ketoiminate ligands and one oxygen atom from the solvated THF molecule to complete a distorted monocapped trigonal prism.展开更多
Scintillators,which convert high-energy radiation into visible light,are indispensable in a wide array of applications,including medical imaging,environmental monitoring,and astronomy[1].However,current high-performan...Scintillators,which convert high-energy radiation into visible light,are indispensable in a wide array of applications,including medical imaging,environmental monitoring,and astronomy[1].However,current high-performance inorganic scintillators,such as ceramics and perovskites,are plagued by issues such as complex manufacturing processes,environmental toxicity,selfabsorption,and stability concerns[2,3].Organic alternatives,on the other hand,suffer from weak X-ray absorption and inefficient triplet exciton utilization[4].Although lanthanide ions uniquely combine high energy conversion efficiency and tunable luminescence for X-ray scintillation,organolanthanide molecules remain underexplored due to a limited understanding of excitonic dynamics within these complexes.展开更多
基金The project is supported by the State Key Laboratory of Polymer Physics and Chemistry in Chinese Acadeny of Scincesthe Joint Foundation of Polymer Chemistry Laboratory of Chinese Academy of Sciencesthe China Petro-Chemical Corporation.
文摘Ind_(2)Y(μ-Et)_(2)AlEt_(2) and Ind_(2)LnN(i-Pr)_(2)(Ln=Y,Yb)were used as a single-component catalyst for the polymerization of acrylonitrile(AN)respectively.The regularity of polymerization of AN and stereoregularity of polyacrylonitrile(PAN)were also studied in both cases.Both catalysts can produce PAN with molecular weight from 10,000 to 30,000.In addition,the catalytic activity and molecular weights were increased by the addition of PhONa.
文摘It was first found that Ind(2)Y(mu -Et)(2)AlEt2 and Ind(2)LnN(i-Pr)(2) (Ln = Y, Yb) exhibit extremely high catalytic activity in the polymerization of methyl methacrylate. The reactions can be carried out over a quite broad range of polymerization temperatures from -30 to 50 degreesC. PMMA with high molecular weight (7.8 x 10(-5)) and high isotacticity (94%) can be obtained by using Ind(2)Y(mu -Et)(2)AlEt2, and narrow molecular weight distribution (M-w/M-n < 1.5) can be obtained by using Ind(2)LnN(i-Pr)(2) (Ln = Y, Yb).
基金Project supported by the Fundacā de Amparo à Pesquisa do Estado de Sāo Paulo and CNPq Conselho Nacional de Desenvolvimento Científico e Teenológico
文摘The synthesis of organolanthanide compounds identified as LnCp^＊（MS）2PzA, Ln = Sm, Tb, Yb （MS = methanesulfonate, Cp^＊ = pentamethylcyclopentadienyl, and PzA = pyrazinamide）, by the reaction of coordination compounds Ln（MS）3（PzA）4 with NaCp in THF was reported. The complexes were formulated according to elemental analyses, complexometric titration with EDTA （%Ln）, and ^1H NMR. IR spectroscopy revealed that PzA coordinates with lanthanide （Ⅲ） ions and methanesulfonate coordinates via oxygen atoms in a non-equivalent manner. In preliminary catalytic studies, these compounds were active in styrene polymerization that used MAO as a cocatalyst with an activity of 12.3 kg PS molSm^-1h^-1. Differential scanning calorimetry （DSC） of polystyrene showed that the polymer was mainly atactic.
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.
文摘The reaction of [(SiMe3)2NC(NC6H11)2]Li with SmCl3 in 2:1 molar ratio in THF gave bis(N,N-cyclohexyl-N创-bis(trimethylsilyl)samarium chloride, [(SiMe3)2NC(NC6H11)2]Sm(m- Cl)2Li(THF)2 1 in 85% isolated yield as pale-yellow crystals. Complex 1 was structurally characte- rized by single-crystal X-ray diffraction analysis at 289(2) K. It crystallizes in monoclinic, space group C2/c with a = 26.886(3), b = 13.677(2), c = 19.465(3) ? b = 120.26(1), V = 6182(2) ?, Z = 4, Mr = 1105.84, Dc = 1.188 g/cm3, F(000) = 2340 and m(MoKa) = 1.150 mm-1. The structure was refined to R = 0.0378 and wR = 0.0885 for 4342 observed reflections with I > 2s(I). The coordination geometry of samarium ion can be best described as a distorted pseudooctahedron.
基金National Natural Science Foundation of China (20632040)
文摘The title complex 1.THF has been synthesized by the reaction of [HO-4,6-di-^tBu- C6H2-2-CH2{CH（IPrNCHCHN）}]C1 with NdCl3 in a 2：1 molar ratio in THF, and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P2dc with a = 9.6501 （14）, b = 16.393（2）, c = 36.745（6） ]A, β = 97.444（4）^o, V= 5763.7（15） ]A^3, Mr= 1124.69, Z = 4, Dc= 1.296 g/cm^3, μ（MoKa） = 1.175 mm-1, F（000） = 2348, the final R = 0.0729 and wR = 0.1762 for 8735 observed reflections with 1 〉 2σ（I）. Complex 1 consists of an anion [NdC15（THF）]^2- and two cations [HO-4,6-di-tBu-C6H2-2-CH2{CH（iprNCHCHN）}]2^＋ to form a layer structure by the interconnection of anions and cations via hydrogen bonding. The central metal Nd in the anionic unit is coordinated by five C1 atoms and one oxygen atom from solvated THF molecule assuming a distorted octahedral geometry.
文摘Anhydrous SmCl 3 reacts with two equal of Li(1,3 tBu 2C 5H 3) to give a complex (1,3 tBu 2C 5H 3) 2Sm( μ Cl) 2Li(THF) 2(C 34 H 58 Cl 2LiO 2Sm, M r =726.99), monoclinic, space group P2 1/n, a=10.615(2), b=21.037(4), c=17.166(3), β=93.60(3)°, V=3825\^7(13) 3, Z=4, D c =1.262Mg/m 3, μ =1.699mm -1 and F (000)=1508, final R= 0.0387 and wR =0.0741 for 5320 observed[ I2σ(I)] reflections. The average Sm-C distance is 2\^73. Sm-Cl1 and Sm-Cl2 distances are 2\^719(2) and 2.697(2), respectively. Two 1,3 tBu 2C 5H 3 ring centroids and two μ 2 bridging chloride atoms around Sm atom form a distorted tetrahedron.
文摘The reactivity of lanthanocene thiolates [Cp2Ln（μ-SEt）]2（Ln = Er, Y, Yb） with PhEtCCO and with PhNCO was examined. Treatment of [ Cp2Ln（μ-SEt）]2 with PhEtCCO gives the α-thiolate-substituted enolate complexes [ Cp2Ln （μ-η^1 ：η^3-OC（SEt）CPhEt）]2（Ln = Yb, Y）, while [Cp2Ln（μ-SEt）]2 react with PhNCO to give the lanthanocene amido derivatives [Cp2Ln（OC（SEt）NPh ）]2（Ln = Er, Yb）. In both cases, the insertion reaction is independent of the stoichiometric ratio and the nature of lanthanides, demonstrating that lanthanocene thiolates are high reactive toward PhEtCCO and PhNCO under the conditions involved. All complexes are characterized by elemental analysis and spectroscopic properties, of which the structures of ytterbium enolate and erbium amido are also determined by X-ray single crystal diffraction analysis, indicating that both of them are centrosymmetric binuclear structures.
文摘Density functional theory (DFT) calculations were carried out on the compounds Cp2Ln-guan for Ln=Y, Lu, Yb, Dy and Gd, [guan=(iPrN)2CN(iPr)2]. The results were compared with the X-ray structures that were available from the literature; the calculations reproduced quite well the experimental structural features in these complexes exhibiting distorted tetrahedron geometry. The calculated evolution of the Ln-guan bond as a function of the cation showed that lanthanide-ligand distances increased with the increa...
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.
基金This work was supported by the National Natural Science Foundation of China (No. 20572014)
文摘（C5H4SiMe2^tBu）2Ln^nBu reacted with 1 equiv, of elemental sulfur in toluene at ambient temperature to yield the corresponding lanthanocene thiolates [（C5H4SiMe2^tBu）2Ln（μ-S^nBu）]2 （Ln = Y （1）, Er （2））. Complexes 1 and 2 have been characterized by elemental analysis, IR, mass spectroscopy and X-ray single-crystal diffraction analysis. Both complexes are of monoclinic with space group P21/c, formula C52H94S2Si4Y2 1 （C52H94S2Si4Er2 2） Mr = 1073.57 （1230.27）, a = 8.495（2） （8.41（2））, b = 26.913（8） （26.67（7））, c = 13.756（4） （13.68（4）） A, α = 90（90）, β = 101.184（5） （101.57（4））, γ = 90 （90）°, V= 3085.1（15） （3007（14）） A^3, Dc = 1.156 （1.359） g·cm^-3, Z= 2 （2）, F（000） = 1144 （1260）, μ = 2.046 （2.951） cm^-1, R = 0.0687 （0.0749） and wR = 0.1306 （0.1507） for observed reflections with I 〉 2σ（I）. X-ray structures of 1 and 2 definitively prove that only one sulfur atom is inserted into the Ln-C（^nBu） bond, forming a thiolate ligand.
文摘The article reviewed the progress in organolanthanide chemistry in China. The contents included the syntheses and molecular structures of organolanthanide complexes, such as tricyclopentadienyl,cyclopentadienyl halides, complexes containing Li-C σ bond,organohydrides, allyl-, cyclooctatetraenyl,tetraenyl-, neutral arene complexes and divalent complexes,and the application to the catalytic and organic reactions including hydrogenation,isomerization, polymerization,dehalogenation,deoxyenation and desulfuration.
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.
基金Supported by Sichuan Application Basic Foundation (2009JY0075)
文摘The title complex L3Y（L = [O-4,6-di-tBu-C6H2-2-CH{CH（iPr2NCHCHN） }]） has been synthesized by the reaction of LiY[N（iPr） 2]4 with H2LCl and LiBu in a 1：3：2 molar ratio at 0 ℃ in THF,and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic,space group P21 with a = 14.3612（16） ,b = 14.7524（14） ,c = 16.898（2） ,β = 105.708（3） o,V = 3446.3（6） A^3,Mr = 1203.50,Z = 2,Dc = 1.160 Mg/m^3,μ（MoKα） = 0.90 mm^-1 and F（000） = 1296. The structure was refined to R = 0.050 and wR = 0.110 for 10213 observed reflections with I 〉 2σ（I） . The Y ion is coordinated to three phenoxo groups and three NHC ligands to form a distorted octahedral geometry. The temperature effect on the reaction leads to the 1,2-benzyl migration of NHC ligand to form the title complex.
文摘Reaction of DyCl 3 with excessive amount of K and indene in THF forms (C 9H 7) 3Dy(THF), which crystallizes in hexagonal system, space group P6 3 with a= b=11.719(5), c=10.167(2) , V=1211(1) 3, M r=580.07, D c =1 590 g/cm 3, Z=2, F(000)=578, μ =31.31 cm -1 . Final R =0.043 and R w =0.055 for 1273 observed reflections with I>3σ(I ). The crystal structure shows that in the title compound the indenyl group is bonded to dysprosium in an η 3+η 2 fashion, and is bent over the C(1) and C(3) axis by 12.7°. Its nodal carbon atoms C(4) and C(9) which are weakly bonded to the metal atom are at distances of 2.92(1) and 2.94(1) , respectively. The average Dy-C( η 3) bond distance is 2.66(1) .
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supported by the National Natural Science Foundation of China(Nos.21072146,21174095 and 21132002)Key Laboratory of Organic Synthesis of Jiangsu,Soochow University(KJS1008)
文摘Three homoleptic lanthanide complexes, [C6H5COCHC（CH3）N（p-CIC6H4）]3Ln（THF）n （n = 0, Ln = Yb （1）; n = 0, Ln = Y （2）; n = 1, Ln = Nd （3））, were synthesized by amine elimination reaction of Ln[N（SiMe3）2]3 with 1-phenyl-3-N-（p-chlorophenylimino）-1-butanone. These com- plexes crystallize in triclinic, space group PI with a = 9.805（3）, b = 14.831（6）, c = 16.075（6） A, a = 111.996（9）, β = 91.570（7）, y = 93.744（6）° V= 2159.4（13） A3, Z= 2, Dc = 1.515 g/cm3, F（000） = 986, μ（MoKa） = 2.396 mm-1, R = 0.0360 and wR = 0.0850 for 9548 observed reflections with I 〉 20（I） for complex 1; a = 9.861（5）, b = 14.852（9）, c = 16.111（9） A, a = 112.362（13）,β = 91.949（11）, y = 93.678（14）°, V= 2173（2） A3, Z= 2, Dc = 1.377 g/cm3, F（000） = 924,μ（MoKa） = 1.570 mm-1, R = 0.0735 and wR = 0.1389 for 8015 observed reflections with I 〉 20（I） for complex 2; and a = 9.308（3）, b = 15.357（3）, c = 17.419（4） A, a = 66.493（13）, β = 88.61（2）, y = 86.664（19）°, V = 2279.4（9） A3, Z= 2, Dc = 1.499 g/cm3, F（000） = 1046,μ（MoKa） = 1.364 mm-1, R = 0.0843 and wR = 0.2280 for 8433 observed reflections with I 〉 20（I） for complex 3. Each central metal in complexes 1 and 2 is six-coordinated by three nitrogen and three oxygen atoms from three β-ketoiminate ligands to give a distorted octahedral geometry, while the central metal in 3 is seven-coordinated by three nitrogen and three oxygen atoms from three β-ketoiminate ligands and one oxygen atom from the solvated THF molecule to complete a distorted monocapped trigonal prism.
文摘Scintillators,which convert high-energy radiation into visible light,are indispensable in a wide array of applications,including medical imaging,environmental monitoring,and astronomy[1].However,current high-performance inorganic scintillators,such as ceramics and perovskites,are plagued by issues such as complex manufacturing processes,environmental toxicity,selfabsorption,and stability concerns[2,3].Organic alternatives,on the other hand,suffer from weak X-ray absorption and inefficient triplet exciton utilization[4].Although lanthanide ions uniquely combine high energy conversion efficiency and tunable luminescence for X-ray scintillation,organolanthanide molecules remain underexplored due to a limited understanding of excitonic dynamics within these complexes.
