Synthesis and Crystal Structure of Bis(tert-butyl-cyclopentadienyl)Erbium Ethoxide, (t-BuCp)_2ErOEt

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.

Reaction of Bis(Methylcyclopentadienyl) Lanthanide Amido Complex with n-Hexyl isocyanate-Synthesis and Characterization of {(MeC_5H_4)_2YbOC(NPh_2)N(n-hexyl)}_2

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.

Molecular Structure of Bicyclopentadienyl (methycyclopentadienyl) Furanto Samarium

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).

Synthesis and Spectroscopic Characterization of Eight Chloro Cyclopentadienyl Titanium Bis (O, O-Dialkyl and Alkylene Dithiophosphate) Compounds

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.

STUDY ON THE REACTIVITY OF TRICARBONYL(PENTAMETHYL-DISILANYL)CYCLOPENTADIENYL MOLYBDENUM ANION

Some reactions of the title anion were studied.By these reactions six molybdenum complexes were prepared.On reac- tion with 1,3-dibromopropane the anion yielded the cyclic carbene complex(η-C_5H_4Si_2Me_5)MoBr(CO)_2CO(CH_2)_2CH_2.The crystal and mole- cular structures of (η-C_5H_4Si_2Me_5)MoBr(CO)_3 and 〔(η-C_5H_4Si_2Me_5)Mo- (CO)_3〕_2 Were determined by X-ray crystallography.

A New Synthetic Route to Di-η~5-Cyclopentadienyl Ytterbium(Ⅱ)Tetrafuranate (η~5-C_5H_5)_2Yb(THF)_2 and Its Crystal Structure

In recent years,the organometallic ehemistry of the lanthanide metals in low oxidation states has beenactively investigated.The synthesis of the low一valent lanthanide eomPlexes has the signifieant meanings ontheory and praeti

Reaction of Substituted Cyclopentadienyl-magnesium-Chloride with Carbonyl Compound ( Ⅰ )——Reaction of (1, 1-Dialkyl-3-Butenyl) Cyclopentadienyl-magnesium-chloride with Ketones

The substituted cyclopentadienyl-magnesium-chloride, obtained by exocyclic addition of 6,6-dialkylfulvene and allyl-magnesium-chloride, reacted with the ketone 3, the product was hydrolyzed and dehydrated to give the 2-(1 ,1-dialkyl-3-butenyl)-6,6-dialkyl-fulvene 5. The structure of 5 was determined by using the 1H NMR spectra of 5 and the adducts of 5 with tetracyanoethylene.

Synthesis and Structure of Di-μ-chlorobis(di-tert-butylcyclopentadienyl) Erbium Chloride

The title compound [(Bu￣tC_5H_4)_2ErCl]_2 crystallized in the triclinic system, space group P1,with a=8.399(2), b=9.429(2), c=12.464(3),a=68.68(2),β= 77.87(2),γ=86.34(2)°,V=897.0(4),Z=1,D_c=1.65g/cm￣3, Mr= 890.28,λ=0.71069,F(000)=470, μ=99. 99 cm-1, T=298 K. Final R= 0.0256, R_w=0. 0294 for 2443 reflections with I>3σ(I_0). The molecule is a dimer in which the two (Bu￣tC_5H_4)_2Er units are connected together by two chlorine atoms. The erbium atom is coordinated by two Bu￣tC_5H_4 groups and two chlorine atoms to form a distorted tetrahedron.

稀土配合物催化异戊二烯和丁二烯聚合的研究进展

异戊二烯和丁二烯单体的聚合物性能优异,在橡胶工业中占据重要地位。稀土金属有机配合物可有效催化共轭双烯烃的选择性聚合。作为一种新兴的催化剂,含茂基配体或多齿非茂基配体的稀土金属配合物逐渐引起了关注。综述了茂基稀土金属催化剂和非茂基稀土金属催化剂对共轭双烯烃的顺式-1,4、反式-1,4和3,4选择性聚合的研究进展。对该领域目前面临的挑战进行了总结,并展望了未来的发展。

SYNTHESIS AND CHARACTERIZATION OF A NOVEL TYPE OF TETRAMETHYLETHYLENE BRIDGED DICYCLOPENTADIENYL LANTHANIDE CHLORIDE COMPLEXES

Although the synthesis of bridged-bicyclopentadienyl lanthanide complexes has been reported, the ethylene-bridged cyclopentadienyl lanthanoid complexes are not yet synthesized. We report here the synthesis and characterization of （CH3）4C2 （C5H4）2 LnCl2.

Synthesis, Reaction and Structures of Functionally Substituted η~5-Cyclopentadienyl Compounds With Cr≡S Triple Bond [η~5-RC_5H_4Cr(CO)_2]_2S (R=CH_3C(O),CH_3O_2C,C-2H_5O_2C,CH_3CH(OH),CO_2H)

[η_5-OH_3C(O)C_5H_4Cr(CO)_2]_2S 1, [η~5-CH_3O_2CC_5H_4Cr(CO)_2]_2S 2 and [η~5-C_2H_5O_2CC_5H_4Cr(CO)_2]_2S 3 were prepared by the reactions of corresponding sodium salts of functional η~5-cyclopentadienyl-tricarbonylchromium anions with SOCl_2. Reduction of 1 with NaBH_4 prdouced [η~5-CH_3CH(OH)C_5H_4Cr(CO)_2]_2S 4, while saponification of 2 followed by acidification and recrystallization from acetone afforded [η~5-HO_2CC_5H_4Cr(CO)_2]_2S·nCH_3C·(O)CH_3 5. 1—5 are a new class of Cr≡S triple bond compounds containing functional organic group on the cyclopentadienyl ring. A single-crystal X-ray diffraction analysis of 1 revealed that it consists of two identical organometallic fragments η~5-CH_3C(O)C_5H_4Cr(CO)_2 joined together by a sulfur atom via triple bonds. The geometry of structural unit Cr≡S≡Cr belongs to linearity and the average triple bond length of Cr≡S is 2.072(?).

Isolation of New Disilanylene-bridged Bis（cyclopentadienyl）tetracarbonyldiiron Complexes and Molecular Structure of [η^5, η^5-C5H4SiMe（SiMePh2）C5H4]Fe2（CO）2（μ-CO）2

1,2-Diphenyl-1,2-dimethyldisilanylene-bridged bis-cyclopentadienyl complex [η^5,η^5-C5H4PhMeSiSiMePh-C5H4]Fe2（CO）2μ-CO）2 （1） was synthesized by a modified procedure, from which the trans-isomer lb that was previously difficult to obtain has been isolated for the first time. More interestingly, two new regio-isomers [η^5,η^5- C5H4SiMe（SiMePh2）C5H4]Fe2（CO）2（μ-CO）2 （2） and [η^5,η^5-C5H4Me2SiSiPh2C5H4]Fe2（CO）2（μ-CO）2 （3） were occasionally obtained during above process, the novel structures of which opened up new options for further study of this type of Si-Si bond-containing transition metal complexes, The molecular structure of 2 has been determined by the X-ray diffraction method.

Synthesis,reactivity and electrochemical properties of substituted cyclopentadienyl cobalt (Ⅲ) complexes

Cyclopentadienyl cobalt complexes (n5-C5H4R)CoLI2 [L = CO,R=-COOCH2CH=CH2 (3); L=PPh3,R=-COOCH2-CH=CH2 (6); L= P(p-C6H4CH3)3,R=-COOC(CH3) = CH2 (7),-COOCH2C6H5(8),-COOCH2CH = CH2 (9)] were prepared and characterized by elemental analyses,1H NMR,IR and UV-vis spectra.The reaction of complexes (n5-C5H4R)CoLI2[L=CO,R=-COOC(CH3)=CH2 (1) ,-COOCH2C6H5(2):L=PPh3,R =-COOC(CH3)=CH2 (4),-COOCH2C6H5(5)] with Na-Hg resulted in the formation of their corresponding substituted cobaltocene (n5-C5H4R)2Co [R= -COOC(CH3) = CH2 (10),-COOCH2C6H5 (11) ].The electrochemical properties of these complexes 1-11 were studied by cyclic voltammetry.It was found that as the ligand (L) of the cobalt (Ⅲ) complexes changing from CO to PPh3 and P(p-tolyl)3,their oxidation potentials increased gradually.The cyclic voltammetry of α,α'-substituted cobaltocene showed reversible oxidation of one electron pro-

环氧有机硅阳离子型光敏预聚物的合成及其光敏性能的研究

合成了环氧有机硅光敏预聚物及阳离子光引发剂甲苯茂铁四氟硼酸盐 ,研究光引发剂种类、预聚物与单体配比、增感剂结构等因素对固化速度的影响 ,发现预聚物体系的感度较高 ,最小感度值为 1 65mJ/cm2 ;

乙基四甲基环戊二烯基铁羰基化合物的合成及晶体结构

将C5Me4HCH2CH3和Fe(CO)5在二甲苯中加热回流,合成了一个新的双核配合物[(η5-C5Me4CH2CH3)Fe(CO)(μ-CO)]2.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线单晶衍射法测定了该配合物的结构,结果表明:晶体属于单斜晶系,C2/m空间群,a=1.170 4(5)nm,b=1.217 9(5)nm,c=0.930 4(4)nm,α=90°,β=115.842(4)°,γ=90°,V=1.193 6(9)nm3,Dc=1.445g/cm3,μ=1.245mm-1,F(000)=542,Z=2,R1=0.024 2,wR2=0.062 0.CCDC号为839243.

溴钼环卡宾配合物的合成及结构

1982年Bailey等以三羰基环戊二烯基钼负离子钠盐与1.

聚乙烯技术新进展

评述了双峰聚乙烯技术,茂金属催化剂和采用液态冷凝技术的乙烯气相聚合工艺的新进展。介绍了生产双峰聚乙烯产品的各种双反应器工艺和单反应器工艺,指出双反应器工艺是目前国际上采用最广泛的工艺,而单反应器工艺目前仍处于开发试验中,是生产双峰聚乙烯产品未来发展方向。液态冷凝气相聚乙烯工艺利用冷凝液体的蒸发潜热及时移走反应热,极大地缓和了反应器散热问题,使得反应器单位体积的聚乙烯产量得到大幅度提高。将液态冷凝技术与超高活性的茂金属催化剂配合使用是当今研究的一个热点。

芳茂铁阳离子聚合光引发剂引发活性研究

研究了 7种不同芳烃结构的芳茂铁四氟硼酸盐作为阳离子紫外光聚合和光固化引发剂在环氧体系中的光引发活性 ,其中 [C5H5Fe 2 ,5 -( CH3) 2 CO-C6 H3]BF4 ( )和 [CH3CO-C5H4 Fe 2 ,4-( CH3) 2 -C6 H4 ]BF4 ( )为新物质 .研究发现 ,这 7个芳茂铁四氟硼酸盐在 3 70和 45 0 nm附近均有较强吸收 ;芳环上引入共轭 C C和共轭 C O使吸收峰发生红移 ,且使摩尔消光系数和感光速度均有所提高 ,更适合于以高压汞灯为辐射光源的长波紫外固化 ;芳茂铁四氟硼酸盐可以引发环氧树脂、脂环族和脂肪族缩水甘油基环氧单分子 ,通过加热或使用有机过氧化物 [如过氧化苯甲酰 ( BPO)

热可逆性共价交联热塑性弹性体的研究

本文以丙烯酸环戊二烯基已酯（ＣＰＤＥＡ）、烯丙基环成二烯（Ａ－ＣＰ）与丙烯酸乙酯（ＥＡ）进行乳液共聚，制得了含环成二烯侧基的共聚物．研究了工艺条件对转化率的影响，测定了共聚物的溶解性能和热转化行为．

Cp_2TiCl_2/n-BuLi催化体系在烯烃加氢反应中的催化活性和稳定性

研究了Ｃｐ２ＴｉＣｌ２／ｎ－ＢｕＬｉ催化体系的构成和Ｔｉ浓度与其催化烯烃加氢反应活性和稳定性的关系．考察了不同结构的烯烃、反应温度和底物浓度对该体系催化性能的影响．结果表明，在高的ｎ（Ｌｉ）／ｎ（Ｔｉ）值和低催化剂浓度时，可得到很高的催化活性．对１－辛烯的催化加氢，其ＴＯＦ（ｉｎｉｔｉａｌ）可高达６３ｓ－１，低温下催化剂效率（ｎ（Ｈ２）／ｎ（Ｔｉ））可达７３００（－２０℃，３５ｍｉｎ）．在低的ｎ（Ｌｉ）／ｎ（Ｔｉ）值和高催化剂浓度时，该催化体系具有较好的稳定性，陈化６９ｈ后，还有一定的活性，ＥＳＲ谱显示有Ｔｉ（Ⅲ）存在．在催化异戊二烯加氢时，该催化剂表现出较好的区域选择性．