茂基稀土邻氨基苯甲酰胺基双负离子配合物的合成及其环胺羰化反应和脒基化反应（英文）

Cp_3Ln与邻氨基苯甲酰胺在甲苯中反应,之后在HMPA和甲苯中结晶,以中等到高收率得到四核稀土有机配合物[CpLn(μ-η~2∶η~2-NHC_6H_4CONH)(μ_3-η~1∶η~1∶η~2-NHC_6H_4CONH)LnCp(HMPA)}2(Ln=Yb,1a;Er,1b;Y,1c)。化合物1与4倍物质的量的Ph NCO在甲苯中反应形成1,3-喹唑啉二氧基(Quo)双负离子稀土配合物[Cp2Ln(μ3-η2∶η2∶η1-Quo)]3Ln(HMPA)2(Ln=Yb,2a;Er,2b;Y,2c),表明化合物1中的Ln-NHAr键和Ar CONH-Ln键能与异氰酸酯分子发生连续加成/胺消除反应,形成1,3-喹唑啉二氧基骨架。但化合物1a~1c与i Pr N=C=NiPr反应,仅得到Ar NH基单加成产物{Cp——2Ln[μ-η~1∶η~1∶η~2-iPrNC(NHiPr)NC_6H_4CONH]}3Ln(HMPA)3(Ln=Yb,3a;Er,3b;Y,3c)。而Cp3Ln与邻氨基苯甲酰胺和i Pr N=C=Ni Pr在甲苯中进行"一锅"反应,则形成双核配合物{CpLn[μ-η~1∶η~2∶η~2-NHCOC_6H_4NC(NHiPr)NiPr]}2(Ln=Yb,4a;Er,4b;Y,4c)。值得注意的是,HMPA能够诱导配合物4发生配体重排反应,转化成化合物3。     

二茂基镧系8—羟基喹啉化合物的合成及其热稳定性研究

通过三茂基镧系化合物Cp_3Ln(Cp=C_5H_5;Ln=Sm,Dy,Ho)与8-羟基喹啉反应(HL),合成了3种新的镧系金属有机化合物,通式为Cp_2LnL(Ln=Sm,Dy,Ho)。经元素分析、红外光谱、X光电子能谱、质谱及分子量测定,推断化合物具有二聚体结构,分子内存在通过喹啉氮原子和氧原子与金属配位而形成的五元螯合环。对化合物的热稳定性进行了研究和比较,发现化合物Cp_2SmL对热不稳定,在180℃以上分解为Cp_3Sm和SmL_3。     

二茚基稀土胺化物催化丙烯腈聚合

用二茚基稀土胺化物Ind2LnN(i-Pr)2(Ln=Y,Yb)作为单组分催化剂催化丙烯腈聚合,研究了催化剂用量、单体浓度及聚合温度对标题化合物的催化活性和所得聚丙烯腈的分子量的影响。提高聚合发应温度可明显提高催化活性,当聚合温度达50℃,单体浓度为5.1mol     

茂基烷氧基稀土化合物[(MeC5H4)2Ln(μ-OCH2CH2NMe2)]2的合成、晶体结构及催化ε-己内酯开环聚合

将N，N-二甲基乙醇胺按1：1的摩尔比与三(甲基环戊二烯)稀土化合物在四氢呋喃(THF)中反应，合成了含N官能基的茂基烷氧基稀土化合物[(MeC5H4)2Ln(μ-0CH2CH2NMe2)]2(Ln=Sm，Y，Nd)。产物经元素分析和红外表征，并测定了钐化合物的晶体结构。结果表明，该化合物具有二个不对称氧桥的双分子结构并存在着由氮原子向中心金属钐经分子内配位而形成的三环骨架，中心金属钐的配位数是九，整个分子呈中心对称。这类配合物对ε-己内酯开环聚合显示良好的催化活性。     

新型二茂稀土烃硫基配合物的合成与表征

本文用三茂基稀土[(C~5H~5)~3Ln(Ln=Ho(1)，Yb(2)，La(3)，Y(4)]与等摩尔的2-巯基嘧啶(HSC:NCH:CHCH:N·)在四氢呋喃溶剂中于室温下反应，合成了四个对空气敏感的二茂稀土嘧啶巯基配合物。产物经元素分析、红外光谱及质谱鉴定确定其组成为：(C~5H~5)~2LnSC:NCH:CHCH:N·THF[Ln=Ho(1)，Yb(2)，La(3)，Y(4)]。     

双核稀土金属烷氧基配合物[Cp~2Ln(μ-OCH~2C≡CH)]~2的合成及表征

由Cp~3Ln(Cp=C~5H~5, Ln=Yb, Gd, Ho)与等摩尔的丙炔醇在四氢呋喃溶剂中,于室温下反应, 合成了三个新的双核稀土金属烷氧基配合物, 产物经元素分析,红外光谱, 质谱等鉴定, 确定三个配合物是通过氧原子桥联的双核配合物, 组成为[Cp~2Ln(μ-OCH~2C≡CH)]~2[Ln=Yb(1), Gd(2), Ho(3)]。     

氯化-甘氨酸六水合稀土固体络合物的合成及红外光谱研究

本文用稀土氯化物与甘氨酸反应制备了标题络合物[Ln(Gly)·6H_2O]·Cl_3(Ln=Nd,Sm,Gd,Er,Yb),测定了络合物的红外光谱,对其主要吸收带进行了归属。红外光谱的研究结果表明,甘氨酸以内盐的形式存在于络合物中,通过羧基与稀土离子配位。水分子也参与了配位。并推测,Nd的络合物为双核络合物,其它稀土络合物具有一维无限长链结构。     

[Ln（EDBP）2（DME）Na（DME）3]（Ln=Er,Yb,Sm）的合成、结构和引发ε-己内酯开环聚合的研究

通过2,2′-亚乙基双（4,6-二叔丁基苯酚）（EDBPH2）的钠盐与硼氢化稀土Ln（BH4）3·3THF（Ln=Er,Yb,Sm）盐交换反应,可以得到离子对形式的三种双金属配合物[Ln（EDBP）2-（DME）Na（DME）3][Ln=Er（1）,Yb（2）,Sm（3）].得到的配合物通过元素分析,FT-IR进行了表征,并对其中的Er配合物进行了X射线单晶衍射表征,确定了其结构.研究结果表明,两分子双酚配体中的四个氧原子及一个乙二醇二甲醚（DME）中的两个氧原子与稀土Er进行了配位,而钠离子作为平衡电荷的形式存在.配合物1～3都能作为单组分引发剂催化ε-己内酯开环聚合.     

含茂基及酰亚胺基镧系金属有机化合物的合成

在室温下由邻苯二甲酰亚胺[phthalimide, H(Pht)]与Cp3Ln在四氢呋喃溶液中反应, 合成了六个新化合物: Cp2Ln(pht),CpLn(pht)2, (Cp=cyclopentadienyl; Ln=Yb, Er, Dy;pht=phthalimido)。它们均经元素分析、红外光谱和质谱鉴定, 为非溶剂化的桥式二聚体结构。     

取代茚基二价稀土配合物催化己内酯开环聚合反应

研究了1-环戊烷基茚基二价镱配合物(1-C5H9C9H6)2Yb(THF)2作为单组分催化剂催化己内酯开环聚合反应, 考察了催化剂用量、聚合反应时间、聚合反应温度对己内酯聚合反应的影响. 结果表明, 配合物(1-C5H9C9H6)2Yb(THF)2对己内酯聚合有较高的催化活性; 温度升高, 聚合反应的转化率增加, 但产物的数均分子量及分子量分布无明显变化; 所得聚合物分子量分布较窄. 其它几种取代茚基稀土配合物也显示出较高的催化活性, 其活性有下列次序: (1-C2H5C9H6)2Sm(THF)2>(1-C5H9C9H6)2Sm(THF)>KSm(1-C5H9C9H6)3(THF)3>(1-PhCH2C9H6)2Sm(THF)2>(1-C5H9C9H6)2Yb(THF)2, 二价钐配合物较二价镱配合物具有较高的催化活性. 通过凝胶渗透色谱法测定了聚合产物的数均分子量及其分布.     

Characterization and reactivity of peralkylated LnIIAlIII heterobimetallic complexes

The heterobimetallic peralkylated complexes [Ln(AlR4)2]n (Ln = Sm, Yb; R = Me, Et) were synthesized by a silylamide elimination route from Ln[N(SiMe3)2]2(THF)2 and an excess of AlR3. The solid-state structure of [Sm(AlEt4)2]n is isomorphous to that of the ytterbium derivative. Polymeric [Yb(AlMe4)2]n was examined by 1H and 13C MAS NMR spectroscopy revealing the presence of distinct bridging methyl groups. The reaction of [Yb(AlMe4)2]n and 1,10-phenanthroline (Phen) afforded the monomeric donor adduct Yb(AlMe4)2(Phen), while the protonolysis reaction with 2 equiv. C5Me5H (HCp*) yielded a separated ion pair of composition [Cp*Yb(THF)(4)][AlMe(4)]. Single-crystal X-ray diffraction data are provided for both ytterbium(II) complexes. Solid-state magnetic measurements (SQUID) were performed on [Sm(AlMe4)2]n, [Sm(AlEt4)2]n, SmI2(THF)2 and Sm[N(SiMe3)2]2(THF)2 showing high effective magnetic moments 3.67micro(B) < micro(eff) < 4.43micro(B).     

Homolysis of the Ln-N (Ln = Yb, Eu) bond. Synthesis, structural characterization and catalytic activity of ytterbium(II) and europium(II) complexes with methoxyethyl functionalized indenyl ligands

The interaction of methoxyethyl functionalized indene compounds (C(9)H(6)-1-R-3-CH(2)CH(2)OMe, R =t-BuNHSiMe(2)(1), Me(3)Si (2), H (3)) with [(Me(3)Si)(2)N](3)Ln(mu-Cl)Li(THF)(3)(Ln=Yb (4), Eu (5)) produced a series of new ytterbium(II) and europium(II) complexes via tandem silylamine elimination/homolysis of the Ln-N (Ln=Yb, Eu) bond. Treatment of the lanthanide(III) amides [(Me(3)Si)(2)N](3)Ln(mu-Cl)Li(THF)(3)(Ln=Yb (4), Eu (5) with 2 equiv. of, 1,2 and 3, respectively, produced, after workup, the ytterbium(II) complexes [eta5:eta1-Me(2)Si(MeOCH(2)CH(2)C(9)H(5))(NHBu-t)](2)Yb(II) (6), (eta5:eta1-MeOCH(2)CH(2)C(9)H(5)SiMe(3))(2)Yb(II) (7), (eta5:eta1-MeOCH(2)CH(2)C(9)H(6))(2)Yb(II)(8) and the corresponding europium(II) complexes [eta5:eta1-Me(2)Si(MeOCH(2)CH(2)C(9)H(5))(NHBu-t)](2)Eu(II)(9), (eta5:eta1-MeOCH(2)CH(2)C(9)H(5)SiMe(3))(2)Eu(II)(10) and (eta5:eta1-MeOCH(2)CH(2)C(9)H(6))(2)Eu(II)(11) in moderate to good yield. In contrast, interaction of the corresponding indene compounds 1, 2 or 3 with the lanthanide amides [(Me(3)Si)(2)N](3)Ln (Ln = Yb, Eu) was not observed, while addition of 0.5 equiv. of anhydrous LiCl to the corresponding reaction mixture produced, after workup, the corresponding ytterbium(II) or europium(II) complexes. All the new compounds were fully characterized by spectroscopic and elemental analyses. The structures of complexes, and were determined by single-crystal X-ray analyses. The catalytic activity of all the ytterbium(II) and europium(II) complexes on MMA polymerization was examined. It was found that all the ytterbium(II) and europium(II) complexes can function as single-component MMA polymerization catalysts. The temperature, solvent and ligand effects on the catalytic activity were studied.     

Postmetallocene lanthanide-hydrido chemistry: A new family of complexes [{Ln{(Me3Si)2NC(NiPr)2}2(mu-H)}2] (Ln = Y, Nd, Sm, Gd, Yb) supported by guanidinate ligands-synthesis, structure, and catalytic activity in olefin polymerization

The new family of Lewis base free hydrido complexes of rare-earth metals supported by guanidinate ligands [{Ln{(Me3Si)2NC(NiPr)2}2(mu-H)}2] (Ln = Y, Nd, Sm, Gd, Yb) was synthesized and structurally characterized. Single-crystal X-ray and solution NMR studies revealed that these complexes are dimeric in both solid state and in [D6]benzene. The dimeric hydrido complexes can adopt eclipsed (Nd, Sm, Gd) or staggered (Y, Yb, Lu) conformations depending on the metal-atom size. Catalytic activity of these [{Ln{(Me3Si)2NC(NiPr)2}2(mu-H)}2] complexes in the polymerization of ethylene, propylene, and styrene has been investigated. Complexes of Sm and Y have high catalytic activity in ethylene polymerization (1268 and 442 g mmol(-1) atm(-1) h(-1), respectively).     

Manipulation of reaction pathways in redox transmetallation-ligand exchange syntheses of lanthanoid(II)/(III) aryloxide complexes

Redox transmetallation/ligand exchange reactions of lanthanoid metals (Ln), Hg(C6F5)2 and HOAr(OMe) (Ar(OMe) = C6H2-2,6-Bu(t)-4-OMe), in thf (tetrahydrofuran) gave, for Ln = Yb, [Yb(OAr(OMe))2(thf)3], and for Ln = Sm, a mixture of [Sm(II)(OAr(OMe))2(thf)3] and mainly [Sm(III)(Ar(OMe))3(thf)] x thf. X-Ray structure determinations show the divalent complexes to have distorted square-pyramidal stereochemistry with transoid thf and OAr(OMe) ligands in the basal plane. Treatment of [Yb(OAr(OMe))2(thf)3] with diethyl ether or PhMe at room temperature gave [Yb(OAr(OMe))2] or [Yb(OAr(OMe))2] x 0.5 PhMe. For lanthanoids Ln = Nd, Er or Y, the reactions with Hg(C6F5)2 and HOAr(OMe) yielded complex product mixtures, from one of which the novel erbium aryloxide fluoride cage [Er3(OAr(OMe))4(mu2-F)3(mu3-F)2(thf)4] x thf x 0.5 C6H14 was isolated. The cage core consists of a triangle of Er atoms joined to two mu3-fluoride ligands and three further mu2-fluorides bridge adjacent Er atoms. One of the Er atoms is six-coordinate with additionally two OAr(OMe) ligands whilst the other two have one OAr(OMe) and two thf ligands and are seven coordinate. Substitution of Hg(C6F5)2 by Hg(CCPh)2 in the redox transmetallation/ligand exchange reactions gave the new derivatives [Ln(OAr(OMe))3(thf)] x thf (Ln = La, Pr, Nd, Sm, Gd, Ho) in good yields whilst Ln = Yb gave [Yb(OAr(OMe))2(thf)3]. Recrystallisation of [Sm(OAr(OMe))3(thf)] x thf from dme (1,2-dimethoxyethane) yielded [Sm(OAr(OMe))3(dme)]. Structural characterisation of [Ln(OAr(OMe))3(thf)] x thf (Ln = Nd, Ho) and [Sm(OAr(OMe))3(dme)] showed monomeric four-coordinate distorted tetrahedral and five-coordinate distorted square-pyramidal complexes respectively. For the smaller lanthanoids Ln = Y, Er or Lu, reactions with Hg(CCPh)2 and HOAr(OMe) gave the mixed aryloxide/alkynide complexes [Ln(OAr(OMe))2(CCPh)(thf)2]. Oxidation of the divalent ytterbium aryloxide [Yb(OAr(OMe))2(thf)3] by Hg(CCPh)2 in thf gave the analogous [Yb(OAr(OMe))2(CCPh)(thf)2]. The erbium alkynide [Er(OAr(OMe))2(CCPh)(thf)2] x 0.25 C6H14 has distorted square-pyramidal stereochemistry with transoid OAr(OMe) and thf ligands in the basal plane and a rare (for Ln) terminal alkynide ligand in the apical position. The reactive Lu-C bond in the [Lu(OAr(OMe))2(CCPh)(thf)2] complexes could be slowly cleaved by free HOAr(OMe) in hydrocarbon solvents, yielding Lu(OAr(OMe))3 species and fortuitous partial hydrolysis of [Er(Ar(OMe))2(CCPh)(thf)2] gave the dimeric [Er(OAr(OMe))2(mu-OH)2]2.     

用非等温DSC曲线确定Ln(NCS)3-·4C3H5CH2NH2的热分解反应机理函数及热分解反应动力学参数

本文利用非等温DSC曲线对十二种镧系元素异硫氰酸盐与苄胺形成的配合物Ln(NCS)3·4C6H5CH2NH2(Ln=La、Pr、Nd、Sm、Eu、Ge、Tb、Dy、Ho、Er、Tm、Yb)进行了非等温动力学研究, 并运用积分法和微分法进行了分析, 推断了它们的热分解反应机理函数。     

Novel lanthanide(II) complexes supported by carbon-bridged biphenolate ligands: synthesis, structure and catalytic activity

[Ln[N(SiMe3)2]2(THF)2](Ln = Sm, Yb) reacts with 1 equiv. of carbon-bridged biphenols, 2,2'-methylene-bis(6-tert-butyl-4-methylphenol)(L1H2) or 2,2'-ethylidene-bis(4,6-di-tert-butylphenol)(L2H2), in toluene to give the novel aryloxide lanthanide(II) complexes [[LnL1(THF)n]2](Ln = Sm, n = 3 (1); Ln = Yb, n = 2 (2)) and [[LnL2(THF)3]2](Ln = Sm (5); Ln = Yb (6)) in quantitative yield, respectively. Addition of 2 equiv. of hexamethylphosphoric triamide (HMPA) to a tetrahydrofuran (THF) solution of 1, 2 and 5 affords the corresponding HMPA-coordinated complexes, [[LnL1(THF)m(HMPA)n]2(THF)y](Ln = Sm, n = 2, m = 0, y = 2 (3); Ln = Yb, m = 1, n = 1, y = 6 (4)) and [[SmL2(HMPA)2]2](7) in excellent yields. The single-crystal structural analyses of 3, 4 and 7 revealed that these aryloxide lanthanide(II) complexes are dimeric with two Ln-O bridges. The coordination geometry of each lanthanide metal can be best described as a distorted trigonal bipyramid. Complexes 1-3, 5 and 7 can catalyze the ring-opening polymerization of epsilon-caprolactone (epsilon-CL), and 1-3, along with 5 show moderate activity for the ring-opening polymerization of 2,2-dimethyltrimethylene carbonate (DTC) and the copolymerization of epsilon-CL and DTC to give random copolymers with high molecular weights and relatively narrow molecular weight distributions..     

稀土与四甘醇醛缩苯丙氨酸Schiff碱配合物的合 成、性能与催化

合成了直链醚-氨基酸新型Schiff碱(四甘醇醛缩苯丙氨酸Schiff碱)及其与稀土新配合物,[Ln~3L~2(NO~3)~2]·(NO~3)~3·nH~2O(Ln=La,Nd,Sm,n=3;Ln=Gd,Dy,Er,Y,n=5),以元素分析、磁化率、红外光谱、^1HNMR等进行了表征,研究了的配位作用,根据预期设想,见到此类配合物在有机溶剂中的溶解性有明显改善。以EPR波谱探讨了配合物的晶体场强,并计算了晶体场参数。此外,发现在不加助催化剂条件下,此类配合物对MMA(甲基丙烯酸甲酯)聚合有一定的催化效果。     

Synthesis, structure and catalytic activity of complexes [Ln(EDBP)2(DME)Na(DME)3](Ln=Er, Yb, Sm) for ring-opening polymerization of ?-caprolactone

Discrete ion-pair complexes [Ln(EDBP)₂(DME)Na(DME)₃] [Ln=Er (1), Yb (2), Sm (3)] have been synthesized by the reaction between sodium salt of 2,2′-ethylidene-bis(4,6-di-tert-butylphenol)(EDBPH₂) and Ln(BH₄)₃·3THF (Ln=Er, Yb, Sm) followed by centrifugation and recrystalization. The complexes were characterized by elemental analysis and FT-IR, and the bonding model of these compounds was confirmed by X-ray single crystal diffraction for complex 1. It was found that four O atoms in two biphenol ligands as well as two O atoms in one ethylene glycol dimethyl ether (DME) molecule connect to the center rare earth metal atom, while sodium exists as counterpart cation to balance the charge. Complexes 1–3 can all be used as single component initiators for the ring-opening polymerization of ɛ-caprolactone.     

2-羟基-3-甲氧基苯甲醛与α-萘胺Schiff碱硝酸稀土配合物的合成与表征

合成邻香兰素(2-羟基-3-甲氧基苯甲醛)与α-萘胺Schiff碱硝酸稀土配合物[LnL~2(NO~3)~2]NO~3(Ln: 镧系元素, L: Schiff碱配体)。配合物由一个中心稀土离子, 两个Schiff碱和三个硝酸根组成, 两个Schiff碱都是氮、氧双配位, 两个硝酸根是双齿配位, 另一硝酸根在配合物外界。中心稀土离子是八配位的, 满足稀土八配位的稳定结构。     

Synthesis of Arenethiolate Complexes of Divalent and Trivalent Lanthanides from Metallic Lanthanides and Diaryl Disulfides: Crystal Structures of [{Yb(hmpa)(3)}(2)(&mgr;-SPh)(3)][SPh] and Ln(SPh)(3)(hmpa)(3) (Ln = Sm, Yb; hmpa = Hexamethylphosphoric Triamide)

A convenient and one-pot synthetic method of lanthanide thiolate compounds was developed. An excess of metallic samarium, europium, and ytterbium directly reacted with diaryl disulfides in THF to give selectively Ln(II) thiolate complexes, [Ln(SAr)(&mgr;-SAr)(thf)(3)](2) (1, Ln = Sm; 2, Ln = Eu; Ar = 2,4,6-triisopropylphenyl), Yb(SAr)(2)(py)(4) (3, py = pyridine), and [{Ln(hmpa)(3)}(2)(&mgr;-SPh)(3)][SPh] (6, Ln = Sm; 7, Ln = Eu; 8, Ln = Yb; hmpa = hexamethylphosphoric triamide). Reaction of metallic lanthanides with 3 equiv of disulfides afforded Ln(III) thiolate complexes, Ln(SAr)(3)(py)(n)()(thf)(3)(-)(n)() (9a, Ln = Sm, n = 3; 9b, Ln = Sm, n = 2; 10, Ln = Yb, n = 3) and Ln(SPh)(3)(hmpa)(3) (11, Ln = Sm; 12, Ln = Eu; 13, Ln = Yb). Thus, Ln(II) and Ln(III) thiolate complexes were prepared from the same source by controlling the stoichiometry of the reactants. X-ray analysis of 8 revealed that 8 has the first ionic structure composed of triply bridged dinuclear cation and benezenethiolate anion [8, orthorhombic, space group P2(1)2(1)2(1) with a = 21.057(9), b = 25.963(7), c = 16.442(8) ?, V = 8988(5) ?(3), Z = 4, R = 0.040, R(w) = 0.039 for 5848 reflections with I > 3sigma(I) and 865 parameters]. The monomeric structures of 11 and 13 were revealed by X-ray crystallographic studies [11, triclinic, space group P&onemacr; with a = 14.719(3), b = 17.989(2), c = 11.344(2) ?, alpha = 97.91(1), beta = 110.30(2), gamma = 78.40(1) degrees, V = 2751.9(9) ?(3), Z = 2, R = 0.045, R(w) = 0.041 for 7111 reflections with I > 3sigma(I) and 536 parameters; 13, triclinic, space group P&onemacr; with a = 14.565(2), b = 17.961(2), c = 11.302(1) ?, alpha = 97.72(1), beta = 110.49(1), gamma = 78.37(1) degrees, V = 2706.0(7) ?(3), Z = 2, R = 0.031, R(w) = 0.035 for 9837 reflections with I > 3sigma(I) and 536 parameters]. A comparison with the reported mononuclear and dinuclear lanthanide thiolate complexes has been made to indicate that the Ln-S bonds weakened by the coordination of HMPA to lanthanide metals have ionic character.