钼铁硫原子簇化合物的合成与结构化学研究II: 以Fe(SR)6为桥的双类立方烷化合物的合成及(Et4N)4[Mo2Fe7S8(SC6H4CH3-m)12].2THF的晶体结构

在乙腈溶液中(Et4N)2[Fe4(SR)10]与(Et4N)2[MoS4]反应半小时生成对氧极为敏感的系列黑色晶状化合物(Et4N)4[Mo2Fe7S8(SR)12](R=C6H5,1;R=C6H4CH3-m, 2;R=C6H4CH3-o, 3;R=C6H4CH3-ρ,4). 2.2THF晶体的分子量为2982.8, 属单斜晶系;空间群为P21/n; a=18.022(2), b=18.375(2), c=22.254(3)A; β=71.04(1)°;V=6969(2)A^3;Dc=1.424g.cm^-^3;Z=2;F(000)=3108.晶体结构用直接法解出,修正至R=0.064. 2.2THF中Mo...Mo'距离为7.234A.     

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-     

烃基取代茚基钌羰基化合物的合成及晶体结构(英文)

配体C9H7R(R=CH2CH2CH3(1),CH(CH3)2(2),C5H9(3),CH2C6H5(4),CH2CH=CH2(5))分别与Ru3(CO)12在二甲苯或庚烷中加热回流,得到了6个双核配合物[(η5-C9H6R)Ru(CO)(μ-CO)]2(R=CH2CH2CH3(6),CH(CH3)2(7),C5H9(8),CH2C6H5(9),CH2CH=CH2(10))和[(η5-C9H6)(H3CH2C)CHCH(CH2CH3)(η5-C9H6)][Ru(CO)(μ-CO)]2(11)。通过元素分析、红外光谱、核磁共振氢谱对配合物的结构进行了表征,并用X-射线单晶衍射法测定了配合物6,9,10和11的结构。     

同多化合物[C_6H_5CH_2NH(CH_3)_2]_4[Mo_8O_(26)]·4H_2O的合成与晶体结构

以MoO3和C6H5CH2N(CH3)2为原料,制得[C6H5CH2NH(CH3)2]4[Mo8O26]·4H2O,并通过扩散法得到无色透明晶体.X射线单晶衍射表明,晶体属三斜晶系,空间群为P墿,晶胞参数a=1.0685(2)nm,b=1.4050(3)nm,c=1.0643(2)nm,α=93.12(3)°,β=110.26(3)°,γ=71.41(3)°,V=1.4179(5)nm3,R=0.0383.     

单茂钪催化剂（C5H5）Sc（CH2C6H4NMe2-o）2合成高顺式窄分布聚丁二烯

合成了6种单茂稀土催化剂Cp’LnR2(THF)n(其中,Cp’=C5H5,C5Me4SiMe3;R=CH2C6H4NMe2-o,CH2SiMe3;Ln=Sc,Y,Lu;n=0或1),并以[Ph3C][B(C6F5)4]为助催化剂,甲苯为溶剂,考察催化剂结构对丁二烯聚合活性,立体选择性,催化剂利用率以及聚合物分子量和分子量分布的影响.通过1H-NMR,13C-NMR,FTIR,GPC以及DSC对聚丁二烯进行表征,结果表明,当Cp’=C5H5,R=CH2C6H4NMe2-o,Ln=Sc,n=0时,催化剂(C5H5)Sc(CH2C6H4NMe2-o)2对丁二烯聚合活性最高,可达9600 kg-polymer/mol-Sc·h,催化剂利用率为45%,聚丁二烯顺-1,4结构含量在96%~98%之间,分子量分布窄,指数在1.3左右;以甲苯或氯苯作为聚合溶剂时,聚合活性最高,聚丁二烯分子量保持窄分布,在所有溶剂中聚丁二烯顺-1,4结构含量均达到96%以上;催化剂聚合活性随温度下降而降低,而聚合物分子量分布有变窄的趋势,温度对聚丁二烯立体选择性无明显影响;当[Bd]/[Sc]摩尔比从500增加到3000时,聚合反应1 min转化率均达到100%,聚丁二烯分子量呈可控线性增大,最高达44.6×104,且均保持聚合物窄分布.DSC谱图表明聚丁二烯Tg为-107℃,当升降温速率为10 K/min时,在-63℃和-8℃附近呈现出明显的冷结晶峰和熔融峰.     

Ethylene polymerization with novel phenoxy-imine catalysts bearing 4-vinylphenyl group

This contribution reports ethylene polymerization behavior of titanium complexes incorporating bis(phenoxyimine) ligands. Six phenoxy-imine Ti(IV) complexes {6-R1-2-[CH=N(2,6-difluoro-3,5-diR2-4-R3Ph)]C6H3O}2TiCl2(1: R1 = H, R2 = H, R3 = H; 2: R1 = H, R2 = H, R3 = 4-vinylphenyl; 3: R1 = CH3, R2 = H, R3 = H; 4: R1 = CH3, R2 = H, R3 = 4-vinylphenyl; 5: R1 = CH3, R2 = F, R3 = H; 6: R1 = CH3, R2 = F, R3 = 4-vinylphenyl) have been synthesized and evaluated for ethylene polymerization using dried MAO(simplified as DMAO) as cocatalyst. An obvious catalytic heterogeneity of Cat 2(Complex 2/DMAO) towards ethylene polymerization was observed, which was illustrated by decreased activity, multimodal molecular weight distribution and partially improved particle morphology comparing with Cat 1. Moreover, Cat 3 exhibits "living" characteristics in the process under certain conditions(25 °C, less than 20 min). Otherwise, the moderate to high ethylene polymerization activity of ca. 105-106 g PE/(mol Ti·h) and high molecular weight(Mw = 105-106) of polyethylene can be obtained by changing the skeleton structure of these complexes.     

丙基联苯酯型液晶的合成:不饱和端基及氧原子对介晶性的影响

本文以对溴苯甲醚为原料制备成格氏试剂,与4-丙基环己酮亲核加成,脱水,Pd/C催化脱氢芳基化,L iPPh2脱甲基得到了4-正丙基-4’-羟基联苯。该联苯与酰氯酯化反应合成了系列丙基联苯酯类液晶化合物C3H7-C6H4-C6H4-OC(O)R。通过差示扫描量热法和热台偏光显微镜对其介晶性研究发现,当R=CnH2n 1(n=3,4)时,化合物无液晶性;但n=5-7、10,C8H16CH=CH2,C8H16C≡CH时,化合物具有SA相;当R=CH2OCmH2m 1(m=2-5),CH2OCH2CH2OCH3时,化合物呈有序度较较高的SB相。这类化合物的液晶相较窄,多在25℃-100℃范围内。TGA测试的化合物热分解温度都高于200℃。     

对苯二甲酸二丙炔醇酯与C02(CO)8、M02Cp2(CO)4和RuC02(CO)11的反应

室温下,对苯二甲酸二丙炔醇酯分别与Co2(CO)8,Mo2Cp2(CO)4和RuCo2(CO)11反应,得到三个有机金属化合物[C6H4-p-(CO2CH2C2H-μ)2][Co2(CO)6]2(1)、[C6H4-p-(CO2CH2C2H)2][RuCo2(CO)9]2(2)和[(HC2CH2OCO)C6H4-p-(CO2CH2C2H-μ)][Mo2Cp2(CO)4](3).研究发现三种金属核对端炔氢的屏蔽作用依次为RuCo2(CO)9＞Co2(CO)6＞Mo2(CO)4Cp2.化合物1的晶体衍射发现,属三斜晶系,空间群PT,a=8.139(2)A,b=8.808(3)A,c=1 1.343(3)A,β=96.260(6)°,V=773.4(4)A3,Z=1,Dc=1.748g@cm-3,R=0.0513,wR=0.1266.     

烃基膦酸单十六烷基酯的结构与其萃取镱(Ⅲ)、镥(Ⅲ)性能的关系

探讨了一类具有高位阻特征的烃基膦酸单十六烷基酯萃取剂R1(R2O)P(O)OH从氯化物介质中萃取Yb(Ⅲ)和Lu(Ⅲ)的结构与性能关系.其中,R1分别为CH2,C2H5,i-C3H7,cyclo-C3H11和C6H5,R2为C4H9CH(C2H5)C2H4CH(C6H13)或C6H13CH(CH3)CH2CH(C6H13).结果表明,这类萃取剂对于Yb,Lu的萃取和分离能力随着其分子中取代基空间位阻的增大而降低.     

三氮唑配合物[Cu2(CH3COO)4(C4H8N4)2]·2CH3CN的合成及晶体结构

Cu(CH3COO)2 和4 氨基 3,5 二甲基 1,2,4 三氮唑反应制得标题化合物的单晶[Cu2(CH3COO)4(C4H8N4)2]·2CH3CN。晶体属三斜晶系 ,空间群 ,a=8.266(2),b=8.585(2),c=10.741(2) ,α=75.58(3),β=88.46(3),γ=86.35(3)°,V=736.7(3) 3 ,Z=1,Dc=1.509g·cm 3,F(000)=346,μ=1.502mm 1 。X 射线衍射结构分析表明 ,Cu2(CH3COO)4(C4H8N4)2 单元是中心对称的双核配合物 ,两个铜原子间距为2.698 。每个金属原子被围成四方锥的配位结构 ,四个乙酸根配体中最近的四个氧原子处在底面上[Cu O=1.965(3)～1.986(3) ] ,一个4 氨基 3,5 二甲基 1,2,4 三氮唑配体位于顶点位置Cu N=2.172 。     

(XNR)_4立方簇合物结构与稳定性的DFT研究

用密度泛函理论(DFT),在B3LYP/CEP-121G水平上,首次对(XNR)_4 [X = C, Si,Ge,Sn,Pb;R = H,CH_3,C(CH_3)_3,Si(CH_3)_3,C_6H_5]立方簇合物的 几何构型、电子结构、振动光谱和化学键性质进行了研究,并对其分子碎片(XNR) _2进行了相同方法的优化计算。结果表明,(CNR)_4对应原5种结构均不能稳定存在 。(XNH)_4对应原5种结构稳定性较低。对于同一取代基R,簇合物的稳定性大小顺 序为：(PbNR)_4>(SnNR)_4>(GeNR)_4>(SiNR)_4>(CNR)_4。     

Syntheses and Crystal Structures of Cobalt(II) Chloride Complexes of 1,3-Bis(pyridyl-4-ylthio)propan-2-one

1 INTRODUCTION Widespread interest of metal-organic coordination compounds has been stirred by their intriguing struc- tural topologies and promising properties[1]. Al- though structural motifs of coordination compounds are mainly defined by metal ions’ coordination pre- ferences and chemical structures of organic ligands including the molecular angle, length and relative orientation of the donor groups[2], numerous other factors such as solvent systems, concentration, coun- terions and e…     

Syntheses, Spectroscopic Properties and Crystal Structures of （2-Cl-C6H4CH2）3SnS2CN（C5H10） and （2-Cl-C6H4CH2）3SnS2CN（C4H9N）

1 INTRODUCTION The chemistry of organotin(IV) complexes was extensively studied due to their biological activity and coordination chemistry[1～7]. More recently, phar- maceutical properties of alkyltin(IV) complexes with dithiocarbamate ligands have bee…     

3-(P-氨基-P-乙氧基酰基)丙酸甲酯类化合物的合成

本文合成了两个未知氯代膦酰基丙酸甲酯和十四个新化合物,初步测定了这些化合物部分样品的生物活性。     

Synthesis and Crystal Structure of Binuclear Copper （Ⅱ） Complex Containing （Dimethylaminomethyl）ferrocene

1 INTRODUCTION Transition metal complexes with ferrocene are of considerable interest in the past fifty years because of their novel structures and special properties[1, 2]. The chemistry of ferrocene and its derivatives has become richer and richer in the last decade. Many complexes containing ferrocenyl have been synthesized and characterized[3～5]. Recently we have reported the synthesis and crystal structure of dibromo[1,1?bis(diphenylphosphino)- ferrocene]cadmium (Ⅱ)[6]. Herein we…     

Catalytic Effect of Cobalt and Iron Complexes Incorporating Bis(2-aldiminoethyl)amine Ligands on Ethylene Oligomerization

IntroductionThe finding of a new promising family ofFe( ) - and Co( ) - based bis( imino) pyridyl cata-lysts for ethylene polymerization and oligomeriza-tion,discovered by Brookhart,Gibson andcoworkers[1— 3 ] ,has intrigued us into researchingthe preparation,the structure and the chemistry ofiron and cobalt complexes incorporating N,N ,N -tridentate ligands.The spectacular enhancement ofthe reactivity of iron and cobalt complexes towardsZiegler- Natta olefin polymerization has been re-po…     

Reaction of Mo(CO)_6 with Alkoxide: Synthesis and Structure of the Mo(0)-OR Complex [Et_4N]_3[Mo_2(CO)_6(μ-OC_6H_4OCH_2C_6H_5)_3]

The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo(0) compound [Et4N]3[Mo2(CO)6(μ-OC6H4OCH2- C6H5)3] 1. 1 crystallizes in monoclinic, space group P21/c with a = 15.359(2), b = 18.378(3), c = 24.952(2), β = 102.268(4)°, V = 6882.3(16) 3, Mr = 1348.34, Z = 4, Dc = 1.301 g/cm3, F(000) = 2832 and μ = 0.424 mm-1. The final R = 0.0606 and wR = 0.1552 for 9396 observed reflections (I > 2σ(I)). 1 contains a [Mo2O3]3- core in triangular bi-pyramidal configuration and each Mo atom adopts a distorted octahedral geometry with three carbon atoms from carbonyls and three μ-O atoms from C6H5CH2OC6H4O- bridging ligands. The Mo…Mo distance is 3.30(8) , indicating no metal- metal bonding. A formation pathway via forming a di-molybdenum(0) di-bridging OR compound [Mo2(μ-OR)2(CO)8]2- has been figured out and the reaction of Mo(CO)6 with alkoxide has also been discussed.     

[(C_5H_4CH_3)_2HoN_4CPh]_2·[(C_5H_4CH_3)(C_5H_5)HoN_4CPh]_2的合成和晶体结构

（C5H4CH3）3Ho和（C5H4CH3）2Ho（C5H5）与5-苯基四唑（HN4CPh）在THF中反应，得到复合产物[（C5H4CH3）2HoN4CPh]2·[（C5H4CH3）（C5H5）HoN4CPh]2，该晶体属三斜晶系，P1空间群，晶胞参数为a=9．386（3），b=13．071（3），c=16.571（2）A，a=86．90（1），β=74．61（2），γ=77.30（2）°，V=1912．2（8）A3，Z=1，Dc=1.602g／cm3，Mr=922．61，μ=41．92cm－1，F（000）=896，最终偏离因子R=0．041，Rw=0．056．晶体数据显示，在同一个晶胞里有两个组成不同的分子，每一个分子都是具有对称中心的四唑基桥二聚体结构，其桥环单元-HoN3HoN3-是平面型的。每个钬原子分别被两个茂基和3个四唑基氮原子配位，形成1个边桥变形四面体构型。     

Synthesis, characterization and ethylene reactivity of 2-diphenylphosphanylbenzamido nickel complexes

Addition of primary amines to N-[2-(diphenylphosphanyl)benzoyloxy]succinimide affords 2-diphenylphosphanylbenzamides, Ph2PC6H4C(O)NHR (R = C(CH3)3, 3; R = H, 4; R = CH2CH2CH3, 5; R = CH(CH3)2, 6). Addition of NiCl(eta3-CH2C6H5)(PMe3) to the deprotonated potassium salts of the amides and subsequent treatment of two equivalents of B(C6F5)3 to the resulting products furnishes eta3-benzyl zwitterionic nickel(II) complexes, [Ph2PC6H4C(O)NR-kappa2N,P]Ni(eta3-CH2C6H5) (R = C6H5, 9; R = C(CH3)3, 10; R = H, 11; R = CH2CH2CH3, 12; R = CH(CH3)2, 13). Solid structures of 9, 11, 13 and the intermediate eta1-benzyl nickel(II) complexes, [Ph2PC6H4C(O)NR-kappa2N,P]Ni(eta1-CH2C6H5)(PMe3) (R = C6H5, 7; R = C(CH3)3, 8) were determined by X-ray crystallography. When ethylene is added to the eta3-benzyl zwitterionic nickel(II) complexes, butene is obtained by the complexes 9-12 but complex 13 provides very high molecular-weight branched polyethylene (Mw, approximately 1300000) with excellent activity (up to 5200 kg mol-1 h-1 at 100 psi gauge).     

Syntheses and Structural Characterization of Dimethyltin Complexs of N-（3-Methoxysalicylidene）-α-amino Acid

Three new dimethyltin complexes of N-(3-methoxysalicylidene)-α-amino acid,(CH3)2Sn(3-CH3O-2-OC6H3CH=NCHRCOO)(R = H,1;CH3,2;(CH3)2CH,3),have been synthe-sized by treating dimethyltin dichloride with the potassium salt of the ligand and characterized by elemental analysis,IR and 1H NMR spectra.The crystal structure of [(CH3)2Sn(3-CH3O-2-OC6H3CH=NCH2COO)(CH3OH)]2 H2O(1a),formed from methanol solution of 1,has been deter-mined.The crystal belongs to the monoclinic system,space group C/2c with a = 20.636(3),b = 7.8854(9),c = 20.668(2) ,β= 113.265(2)°,V = 3089.7(6) 3,Z = 4,Dc = 1.707 g/cm3,= 1.675 mm-1,F(000) = 1592,R = 0.0301 and wR = 0.0841.In complex 1a,the tin atom is six-coordinate and possesses a distorted [SnC2NO3] octahedral geometry with the two methyl groups occupying the trans positions.The weak Sn O interactions and intermolecular hydrogen bonds connected the molecules into an infinite chain.