Some Rare Earth Metallic Organohydrides with Biindenyl as the Ligand

Introduction It is well known that organometallic hydrides of rare earth metals are the catalysts and reducing reagents for the catalysis polymerization of alkenes and the catalysis hydrogenation of alkenoalkynes. There are four methods for the syntheses of organometallic hydrides of rare earth metals:（1） the thermal atomization of metals, i.e., the interaction of a rare earth metal with alkenes with a terminal alkyne;（2） the Ln—Cσ bond is broken with H;;（3） metal-

Polymerization of Dimethylaminoethyl Methacrylate Catalyzed by Substituted Indenyl Lanthanide(II) Complexes

The polymerization of dimethylaminoethyl methacrylate （DMAEMA） catalyzed by the 1-cyclopentylindenyl lanthanide （Ⅱ） complex （1-C5H9C9H6）2Yb （THF）2 was investigated. The results indicated that the complex （1- C5H9C9H6）2Yb （THF）2 as a single component catalyst showed high activity. The conversion of the polymerization and the molecular weight of the polymer were affected by temperature, time, amount of catalyst and solvent in the polymerization process. The catalytic activity of （1-C5H9C9H6）2Yb （THF）2 enhanced significantly when a small amount of polar solvent THF was added into the polymerization system in which toluene was selected as the solvent. The optimal temperature of polymerization was about 0 ℃. Other modified substituted indenyl lanthanide （Ⅱ） complexes also showed good catalytic activity. The order of catalytic activity of the complexes was as follows： （1-C5H9C9H6）2Sm（THF）≈ （1- C2 H5 C9H6 ）2 Sm（THF）2 〉 （1 -C5 H9 C9 H6 ）2 Yb（THF）2 〉 （1 -PhCH2 C9 H6 ）2 Sm（THF）2. The steric regularity of p oly （dimeth- ylaminoethyl methacrylate） （PDM AEM A） was characterized by 1H NM R spectra. The polymerization provided syndio- tacticity-rich PDM AEM A. The molecular weight and the molecular weight distribution of PDM AEM A were measured by gel permeation chromatography.

Synthesis and Crystal Structure of {η~5:η~1-[(2-Methoxyphenyl)-isopropyl]-indenyl}(dimethoxyethylene)lithium1

The title compound {η^5：η^1-[（2-MeOC6H4）C3H6]CgH6}Li（DME） （DME=1,2-dimethoxy-ethylene） was synthesized by the treatment of 3-[（2-methoxyphenyl）-isopropyl]-indene with 1 equiv, of n-BuLi followed by the recrystallization from a mixed solution of toluene and DME. The compound crystallizes in orthorhombic system, pace group Pbca with a=14.5677（3）, b=15.54670（10）, c=18.7498（3）A°, Z=8, V=4246.45（11）A°^3, Dc=1.127 g/cm^3 and μ（MoKα）=0.072 mm^-1. The coordination geometry can be described as a distorted tetrahedron.

SYNTHESIS， STRUCTURE AND THERMOREANGEMENT OF TRTRA METHYLDISILANDIYL BIS（1－INDENYL） TETRACARBONYL DI－IRON

The title compound (Me2SiSiMe2)[(η5-1-indenyl)Fe(CO)]2(μ-CO)2 was preparedby the reaction of 1 .2-bis(1-indenyl)tetramethyldisilane and Fe(CO)5 in retluxing heptane inrefluxing xylene can be converted into [Me2Si(η5-1-indenyl ) Fe(CO)2]2.The pure transisomer 2t was obtained and its crystal and molecular structure was determined by X-raydiffraction.

Synthesis and Crystal Structure of an Indenylnickel(II) NHC Complex (Ind)NiBr(1,3-bisbenzylimidazol-2-ylidene)

The complex （Ind）NiBr（1,3-bisbenzylimidazol-2-ylidene） （Ind = indenyl） 1 has been prepared in ca. 65% yield via the reaction of （Ind）2Ni with an equivalent of 1,3-bis-benzylimidazolium bromide in THF/CH2Cl2 at 45℃, supported by elemental analysis, NMR spectroscopy and X-ray crystal determination. The crystal belongs to the triclinic system, space group Pi with a = 7.072（1）, b = 11.264（2）, c = 14.541（3）°A, α = 102.21（3）,β = 93.44（3）,γ = 90.81（3）°, V = 1129.7（4）°A^3, Z = 2, Mr = 502.08, Dc = 1.476 g/cm^3, F（000） = 512, μ= 2.642 mm^-1, R = 0.0490 and wR = 0.1137 for 3913 observed reflections （I〉 2σ（I））. The center nickel atom is coordinated by a bromide ligand, a carbene carbon and three carbon atoms of the five-membered indenyl group to form either a highly distorted square pyramid or a highly distorted square plane.

Synthesis and Structure of Tetrahydrofuran Adduct of Tris(indenyl)dysprosium

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) .

Ethylene-bridged Indenyl-fluorenyl Metallocene Complexes for Efficient Preparation of Allyl-terminated Propylene Oligomers and Polymers via Selective β-Methyl Transfer

Four C_1-symmetric ansa-metallocene complexes, C_2H_4(Ind)(2,7-~tBu_2-Flu)ZrCl_2(4), C_2H_4(3-Bn-Ind)(2,7-~tBu_2-Flu)ZrCl_2(5),C_2H_4(3-Bn-Ind)(3,6-~tBu_2-Flu)ZrCl_2(6), and C_2H_4(3-Bn-Ind)(2,7-~tBu_2-Flu)HfCl_2(7), were synthesized and characterized. The structures of complexes 4, 5, and 7 were further determined via X-ray diffraction studies. Upon activation with modified methylaluminoxane(MMAO) or Al^iBu_3/[Ph_3C][B(C_6F_5)_4](TIBA/TrB), most of these complexes showed high efficiency in catalyzing propylene oligomerization/polymerization to afford products dominantly with allyl terminals via selective β-methyl transfer(β-Me transfer). The introduction of 3-benzyl group on the indenyl ring of the complexes was found to be crucial in enabling highly selective β-Me transfer during the polymerization process, leading to selectivities up to 89% obtained by zirconocene complexes 5 and 6, and up to 91% obtained by hafnocene complex 7. Detailed chain-end analysis by ~1H-NMR, ^(13)C-NMR, and MALDI-TOF mass spectroscopy revealed that the allyl chain-ends of the polymeric products resulted from a selective β-Me transfer process after two successively primary insertions of the monomer. Further studies concerning the dependence of chain release selectivity as well as the molecular weight of products on monomer concentration suggested that both β-Me transfer(major) and β-hydrogen transfer(β-H transfer)(minor) mediated by 5/MMAO and 6/MMAO systems may mainly operate in a bimolecular pathway.

Copolymerization of Ethylene/1-hexene and Polymerization of Propylene with Cp-indenyl Zirconium Complexes

Complexes （R^1Cp）（R^2Ind）ZrCl2, the catalysts previously reported active for ethylene polymerization showed high activity in ethylene/1-hexene copolymerization and propylene polymerization in the presence of MAO. The content of 1-hexene in copolymers ranged from 1.2% to 3.2%. In propylene polymerization the complex 1 showed the highest activity, up to 1.2×10^6 g of polypropylene per mol of catalyst per hour. Based on the analysis of NMR spectral data, the relationships between complex structures and polymerization results were explored.

Indenylnickel（Ⅱ） Halides for the Polymerization of Styrene in the Presence of NaBPh4/PPh3

The catalytic activity of a series of indenylnickel（Ⅱ） halides： （1-R-Ind）Ni（PPh3）X （R=ethyl, cyclopentyl and benzyl, while X=Cl, Br and I）, towards styrene polymerization was studied in the presence of NaBPh4 and PPh3. The catalytic property of these halides was related to the substituent group on the indenyl ligand and the halogen atom bonded to the metal atom. Among them, the （1-Et-Ind）Ni（PPh3）Cl/NaBPha/PPh3 system showed the highest activity for the polymerization of styrene, and the polystyrene obtained was a syndio-rich （rr triad） atactic polymer with Mn values in the range of 103--104. The mechanism of the styrene polymerization initiated by the （1-Et-Ind）Ni（PPh3）Cl/NaBPha/PPh3 system was studied.

Synthesis of Substituted Indenyl Lanthanide Chloride and Molecular Structure of [(C_5H_9C_9H_6)_2Yb(μ-Cl)_2Li(Et_2O)_2]

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.

取代茚基稀土配合物/添加剂体系催化丙烯腈聚合

研究了取代茚基稀土配合物 /添加剂体系对丙烯腈的聚合 ,发现季胺盐及芳氧钠是取代茚基二价稀土配合物催化丙烯腈聚合的有效添加剂 ,其中Me3NC1 6 H33Br效果最好 ,5种二价稀土配合物 (C5H9C9H6 ) 2 Yb (THF) 2 ,(C5H9C9H6 ) 2 Sm (THF) 2 ,KSm (C5H9C9H6 ) 3(THF) 3,(PhCH2 C9H6 ) 2 Sm(THF) 2 和 (CH3CH2 C9H6 ) 2 Sm (THF) 2 与Me3NC1 6 H33Br构成的催化体系对于丙烯腈聚合都显示出好的催化活性。对(C5H9C9H6 ) 2 Yb(THF) 2 /Me3NC1 6 H33Br体系而言 ,在丙烯腈中当催化剂用量为 2× 10 - 5mol·g - 1时 ,丙烯腈聚合的最大转化率为 61%。

二(1-正丁基茚基)四羰基二钌的合成与晶体结构

由C9H6-n-BuH与Ru3(CO)12在二甲苯中加热回流,合成了一个新的双核配合物(η5-C9H6-n-Bu)2Ru2(CO)4.通过元素分析、红外光谱、核磁共振氢谱对其结构进行了表征.用X射线单晶衍射法测定了(η5-C9H6-n-Bu)2Ru2(CO)4的结构,结果表明:晶体属于三斜晶系,Pī空间群,a=0.8880(5)nm,b=1.2337(8)nm,c=1.3235(8)nm,α=83.054(12)°,β=76.683(10)°,γ=77.036(12)°,V=1.3713(15)nm3,Dc=1.588g?cm-3,μ=1.134mm-1,F(000)=658,Z=2,R1=0.0993,wR2=0.2459.

取代茚基二价稀土配合物催化甲基丙烯-酸N,N-二甲胺乙酯的聚合

研究了取代茚基二价稀土配合物(1-C5H9C9H6)2Yb(THF)2催化甲基丙烯酸-N,N-二甲胺乙酯的聚合。结果表明,配合物(1-C5H9C9H6)2Yb(THF)2作为单组分催化剂对甲基丙烯酸-N,N-二甲胺乙酯的聚合显示出较高的催化活性,反应温度、时间、催化剂用量及溶剂性质对聚合反应转化率和产物分子量有较大影响,在以甲苯为溶剂的催化体系中加入少量的极性溶剂THF,聚合活性有明显提高。其他几种取代茚基稀土配合物也显示出高的催化活性,其活性有下列次序:(1-C5H9C9H6)2Sm(THF)≈(1-C2H5C9H6)2Sm(THF)2>(1-C5H9C9H6)2Yb(THF)2>(1-PhCH2C9H6)2Sm(THF)2,二价钐配合物较二价镱的相应配合物具有较高的催化活性。聚合产物的分子量及分子量分布通过凝胶渗透色谱法表征,立构规整性由1H NMR谱表征,所得聚合物以间同立构为主。

柄型金属有机化合物（Ⅰ）──硅桥联二（1－茚基）和四氢茚基钛化合物的合成及结构

通过１，３－二（１－茚基）四甲基二硅氧烷的双锂盐与ＴｉＣｌ４·２ＴＨＦ反应制得硅桥联二（１－茚基）钛化合物（Ｍｅ２ＳｉＯＳｉＭｅ２）［Ｉｎｄ］２ＴｉＣｌ２（１），对其催化氢化得到相应的四氢茚基化合物（Ｍｅ２ＳｉＯＳｉＭｅ２）［ＩｎｄＨ４］２ＴｉＣｌ２（２）。对化合物１和２的单晶进行了Ｘ射线衍射结构分析，它们的晶体都属单斜晶系，Ｐ２１／ｎ空间群。

二茚基二芳氧基锆催化乙烯齐聚

Compounds Ind 2Zr(OC 6H 4 p Me) 2, Ind 2Zr(OC 6H 5) 2, Ind 2ZrCl 2 and Cp 2Zr(OC 6H 4 p Me) 2 have been synthesized and formed respective catalysts A、B、C、D with Et 2AlCl. The effects of polymerization temperature, time and catalyst aging temperature on the catalytic activities and selectivities of the catalysts in ethylene oligomerization have been investigated. The order of the catalytic activity of the catalysts was A>B>C>D. Under optimal reaction conditions the activity of catalyst A was 1666 g/g·h (oligomer mass obtained by one gram Zr in catalyst per an hour) with selectivity of 92 7% for C = 4～C = 10 olefins and 86 0% for C = 4～C = 10 linear α olefins.

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.

茚基钠/四氢呋喃体系引发丙烯腈聚合的研究

以茚基钠为引发剂,对丙烯腈在四氢呋喃中的聚合反应进行了研究,考察了引发剂用量、单体与溶剂配比、反应时间及反应温度对丙烯腈聚合的影响,并用粘度法对聚合产物的粘均分子量进行了表征。结果发现茚基钠/四氢呋喃体系对丙烯腈聚合反应具有一定的引发活性,且随着引发剂用量增加聚合反应转化率增大,聚合产物的粘均分子量下降;当单体用量一定时,溶剂的量越多,聚合反应的转化率越低,而聚合产物的粘均分子量却越大;反应时间在1 h之内,延长反应时间,转化率和粘均分子量都增大;反应温度对聚合反应转化率影响不大,但对聚合产物粘均分子量有明显影响。

二(1-环戊烯基茚基)四羰基二钌的合成、晶体结构及热稳定性研究(英文)

由6,6-四亚甲基苯并富烯C9H6C(CH2)4与Ru3(CO)12在二甲苯中加热回流,合成了一个钌配合物[((η5-C9H6)C(C4H7))2Ru2(μ-CO)2(CO)2]。通过元素分析、红外、热重、核磁共振进行了表征及研究。用X射线单晶衍射法测定了[((η5-C9H6)C(C4H7))2Ru2(μ-CO)2(CO)2]的结构,结果表明:晶体属于单斜晶系,P21/c空间群,a=0.757 1(13)nm,b=1.577 7(3)nm,c=1.107 3(19)nm,β=90.07(2)°,V=1.322 6(4)nm3,Dc=1.699 g.cm-3,μ=1.179 mm-1,F(000)=676,Z=2,R1=0.030 5,wR2=0.072 4。

取代茚基二价稀土配合物催化甲基丙烯酸甲酯/甲基丙烯酸-N,N-二甲胺乙酯共聚反应的研究

研究了取代茚基二价稀土配合物(C5H9C9H6)2Yb(THF)2作为单组分催化剂,催化DMAEMA/MMA的共聚反应。结果表明,(C5H9C9H6)2Yb(THF)2对DMAEMA/MMA的共聚反应具有较高的催化活性,温度对共聚反应影响明显,单体配比对共聚反应的转化率影响不大,几种取代茚基二价稀土配合物都显示出较高的催化活性。其活性次序为:(C5H9C9H6)2Sm(THF)>(C2H5C9H6)2Sm(THF)2>(C5H9C9H6)2Yb(THF)2>KSm(C5H9C9H6)3(THF)3>(PhCH2C9H6)2Sm(THF)2。对聚合产物进行了热分析的表征,发现产物为两种单体的无轨共聚物。通过核磁共振技术确定了共聚物中两种单体所占的比例,并测定了(C5H9C9H6)2Yb(THF)2催化DMAEMA/MMA的共聚反应的竟聚率,其竟聚率为r1=0.98,r2=0.71。

三亚甲基桥联双茚基钐二苯胺化物催化己内酯聚合

研究了三亚甲基桥联双茚基钐二苯胺化物(C_9H_6CH_2CH_2CH_2C_9H_6)SmNPh_2作为单组分催化剂催化ε-己内脂开环聚合反应,考察了催化剂用量、聚合反应时间和聚合反应温度对ε-己内酯聚合反应的影响。结果表明,配合物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,但产物粘均分子量降低。通过粘度法对聚合产物的粘均分子量进行了表征。