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1.
本文推导了[η]线/[η]环与S0环/S0线和D0环/D0线的关系式并通过实验验证了[η]线/[η]环与S0环/S0线关系式。 相似文献
2.
采用密度泛函方法(DFT)在M06-2X/def2-TZVPP//B3LYP/def2-TZVPP+ZPE水平下, 对以开环的(η5-C5H7)2Ru为前驱体生成闭环(η5-C5H5)2Ru的各种可能的反应路径进行了详细的研究. 最终确定其反应机理为: (η5-C5H7)2Ru的一个η5-C5H7发生端碳成键的成环反应形成(η3-C5H7)Ru(η5-C5H7), 经过两步氢原子迁移到Ru原子上, 之后脱掉一个氢气分子形成(η5-C5H5)Ru(η5-C5H7), 而后另一个η5-C5H7再重复成环并进行两步氢迁移以及氢气分子消除而得到最终的产物(η5-C5H5)2Ru. 相似文献
3.
碳锗双桥连二环戊二烯(Me2C)(Me2Ge)(C5H4)2(1)与五羰基铁在回流甲苯及二甲苯中的反应,得到正常的Fe-Fe键化合物(Me2C)(Me2Ge)[(η5-C5H3)Fe(CO)]2(μ-CO)2(3)和脱锗桥产物(Me2C)[(η5-C5H4)Fe(CO)]2(μ-CO)2(4)以及一个结构新颖的化合物(Me2C)[(η5-C5H3)[(Me2Ge)Fe(CO)2](η1,η5-C5H3)[Fe(CO)2](2).用X射线衍射分析測定了化合物3的晶体结构,并提出了可能的生成机理. 相似文献
4.
张 《高等学校化学学报》1999,20(9):1329-1333
利用苯乙炔或丙炔醇与[Mo(CO)2(η5-C5H4R1)]2[R1=C(O)Me,C(O)OEt,C(O)Ph]的反应合成了6个新的炔烃配位的双钼化合物[Mo(CO)2(η5-C5H4R1)]2(μ-η2,η2-(CH=CR2)[R1=C(O)Me,R2=Ph,1;R1=C(O)OEt,R2=Ph,2;R1=C(O)Ph,R2=Ph,3;R1=C(O)Me,R2=CH2OH,4;R1=C(O)OEt,R2=CH2OH,5;R1=C(O)Ph,R2=CH2OH,6],并对这些化合物进行了C/H元素分析,IR,1HNMR等表征.晶体X射线衍射分析结果表明,化合物1属单斜晶系,P21(#4)空间群,晶胞参数a=0.7671(2)um,b=0.8365(2)nm,c=1.8308(3)nm,β=98.34(1)°,V=1.1623(5)um3,Z=2,Dc=1.772g·cm-3,F(000)=616,R=0.041,Rw=0.045. 相似文献
5.
灵芝菌丝体多糖的化学组成和溶液性质 总被引:7,自引:0,他引:7
用磷酸盐缓冲液在80℃时从灵芝菌丝体中提取出多糖-蛋白质缀合物LM-A.成分分析表明,GLM-A主要由葡萄糖组成,蛋白质含量为13%.GLM-A在1∶1水稀释的饱和镉乙二胺溶液中30℃时的特性粘数[η]和均方根旋转半径〈S2〉1/2的分子量依赖关系分别为[η]=5.1×10-2Mw0.06(cm3·g-1)和〈S2〉1/2=3.9×10-2Mw0.50(nm).按照Yamakawa-Fujii-Yoshizaki蠕虫状圆筒模型的粘度理论和Bohdanecky表达式,求得GLM-A的分子参数为:单位围长摩尔质量ML=(530±10)nm-1,持久长度q=(2.8±0.2)nm.链直径d=0.75nm.实验结果表明,GLM-A在该溶液中为无规线团构象. 相似文献
6.
新型桥联双四面体簇合物的合成与表征 总被引:2,自引:0,他引:2
利用(μ3-CCO2Et)Co3(CO)9与单阴离子试剂[Mo(CO)3(η5-C5H4R)]-[R=H,C(O)Me]的反应合成了2个新的含CCo2Mo骨架的簇合物(μ3-CCO2Et)Co2Mo(CO)8(η5-C5H4R)[R=H(1);R=C(O)Me(2)],进而用其与双阴离子试剂{-M(CO)3[η5-C5H4C(O)]}2-1,4-C6H4[M=Mo,W]反应合成了4个双四面体簇合物{(μ3-CCO2Et)CoMoM(CO)7(η5-C5H4R)[η5-C5H4C(O)]}2-1,4-C6H4[M=Mo,R=H(3);M=Mo,R=C(O)Me(4);M=W,R=H(5);M=W,R=C(O)Me(6)].这6个化合物的C和H元素分析,IR,1HNMR等表征都与其结构一致.晶体X射线衍射分析表明,化合物2属单斜晶系,C2/c空间群,晶胞参数a=1.1264(3)nm,b=1.1879(3)nm,c=3.3565(10)nm,β=93.320(5)°,V=4.484(2)nm3,Z=8,Dc=1.867g·cm-3,F(000)=2480,R=0.0369,wR=0.1150. 相似文献
7.
通过亲核取代反应, 在2,2'-联苯二酚氧基环氯磷腈母体N3P3(O2C12H8)2Cl2 (1)和N3P3(O2C12H8)Cl4 (2)上引入2-醛基吡啶与对胺基苯酚形成的席夫碱侧基, 合成了两种新型环磷腈化合物N3P3(O2C12H8)2(p-O-Ph-N=C-Py)2 (3)和N3P3(O2C12H8)(p-O-Ph-N=C-Py)4 (4), 这些化合物是一类能形成配合物的多齿配体. 通过元素分析, IR, 1H NMR, 31P NMR和TOFMS确定其结构, 研究了它们的吸收光谱和荧光光谱. H+和Cu+离子对其光谱性质的影响研究表明两种化合物的吸收和荧光光谱对H+和Cu+离子异常敏感, 因而在作为这些阳离子的荧光探针方面具有应用前景. 相似文献
8.
在溶剂热条件下,以不对称三羧酸5-(6-羧酸-2-萘基)-间苯二羧酸(H3L)为配体合成了2个镉的金属-有机骨架化合物:{[Cd3L2(H2O)3]·6DMF}n(1)和{[Cd3L2(H2O)4]·3DMA}n(2)。通过X射线单晶衍射,粉末衍射,热重和红外光谱进行了结构表征。结构分析表明,1和2形成3,6-连接的三维结构,其拓扑符号分别为:(45.64.86)(43)2和(612.83)(63)2。此外,还对2个化合物进行了荧光分析。 相似文献
9.
具有不同电荷和手性的Co(Ⅲ)配合物跨人红细胞膜的动力学研究 总被引:6,自引:0,他引:6
研究了4种不同电荷的Co(Ⅲ)金属配合物跨人红细胞膜的动力学,并测定了它们跨人红细胞膜的一级反应动力学速率常数,发现[Co(C2O4)3]3-的跨膜速率明显高于[Co(en)3]3+,[Co(en)2(C2O4)]+和[Co(en)(C2O4)2]-,后3种配合物的跨膜速率常数随正电荷的减少略有增加,跨膜机制为简单扩散.[Co(C2O4)3]3-的跨膜速率受阴离子通道抑制剂DIDS明显抑制,抑制率为51.95%,推测其跨膜机制为部分经阴离子通道协同简单扩散过膜.人红细胞摄入L-[Co(C2O4)3]3-的速率明显大于D-[Co(C2O4)3]3-,显示了一定的手性选择性. 相似文献
10.
本文用X-射线衍射法测定了(η5CH9C5H4)5H1(OC6H9Cl3-2,6)2的晶体和分子结构.晶体结构属单科晶系,空间群为P21/c,晶胞参数为a=17.010(2)Å,b=8.577(1)Å,C=16.313(3)Å,β=101.52(3)°,晶胞内分子数Z=4.分子内有非结晶学二次旋转轴对称性,铪原子周围的两个甲基环戊二烯基和两个氧原子构成一个变形四面体.两个环戊二烯基的平面夹角为125.33°.氧-铪-氧键角为103.71°.铪-氧键长为2.004-2.022Å,较铪-氧单键键长为短,表明具有部分双键特性. 相似文献
11.
Two correlation stations,.requ.ring/requ.open=1/(η)open/[η]ring1/3 and fring/ fopen-1/([η]open/[η]ring1/3 of the ring shaped and linear shaped polymer coils with the same monomer and molecular weight in a dilute solution have been derived.If leave excluded volume effect out of consideration,there are 相似文献
12.
Edward W. Abel Elizabeth S. Blackwall Michel L. Creber Peter J. Heard Keith G. Orrell 《Journal of organometallic chemistry》1995,490(1-2):83-88
The hybrid S/N/S donor ligands 2,6-bis(methylthiomethyl)pyridine (L1) and 2,6-bis(p-tolylthiomethyl)pyridine (L2) react with the [M(CO)5(THF)] (M = Mo or W) compounds to form complexes of general formula [M(CO)4L] (M = Mo, L = L2; M = W, L = L1 or L2), where both L1 and L2 act in a S/N bidentate chelate fashion. In solution, these complexes undergo three fluxional processes, viz. inversion at the coordinated S atom, S1–S2 switching, and combined inversion and S1–S2 switching, leading to an interconversion of the four possible permutational isomers. Energy barriers for all three processes have been evaluated by standard one-dimensional band-shape analysis techniques. The mechanism of the S1–S2 switch is discussed. 相似文献
13.
Since the trinuclear molybdenum cluster compound Mo3S4(DTP)3(μ-DTP)(L) (DTP=diethyldithiophosphate, L=loosely-coordinated ligand) was reported[1],a large number of monomeric trinuclear molybdenum derivatives have been synthesized from it by its diverse substitution reactions[2]. This reaction provides a useful route to design cluster complexes with specific functions. By the reaction with α, ω-dicarboxylates, we successfully synthesized the first oligomer containing two incomplete cubane-type[Mo3S4] cores formulated as[Mo3S4(DTP)3(DMF)]2[η2-μ-OOC(CH2)3COO-μ-η2]) whose molecule structure is as follows: 相似文献
14.
(η5-C6H5)2Nb[CH2Si(CH3)3]2has been prepared and characterized by X-ray diffraction method and solution and frozen-glass EPR.The compound crystallizes in a monoclinic space group P21/Owith lattice parameters a=13.291(Å),b=12.406(Å),σ=13.901Å,β=115.40,V=2070Å5and Z=4 Full-matrix least-squares refinement of the diffractometry data led to final discrepancy indices of K(F0)=0.043,R(F02)=0.057,Rw(F02)=0.071.From computer simulation of the frozen-glass spec trum of the compound,the principal components of the g and Ttensors are gx=1.9840.gy=2.0075,gz=2.0020,Tx=-89.2G,Ty=-136.9G,Tz=-50.0G.The observed anisotropy for the hyperfine interaction arises from the admixture of 4dz2 and 4dx2-y2 character in the HOMO.The ratio of mixing coefficients a2/b2=10.3. 相似文献
15.
本文研究了1-苯基-3-甲基-4-苯甲酰基吡唑啉酮-5(PMBP)与丁基膦酸二丁酯(DBBP)或磷酸三丁酯(TBP)的氯苯溶液在硝酸介质中对铽(Ⅲ)的协同萃取。测得了萃合物的组成及其萃取平衡常数,讨论了萃合物的可能结构式及协同萃取机理。 相似文献
16.
A nonanuclear Cu4^ⅡTi5^Ⅳheterometallic cluster,[Ti5 Cu4 O6(ba)(16)](1,Hba=benzoic acid)was synthesized in one-pot reaction under the solvothermal condition.The metallic skeleton 1 contains a Ti5 core constructed from two vertex-shared Ti3 triangles and four separated Cu atoms outside which are connected together byμ3-O^2- ions.Total 16 ba ligands adoptμ2-η^1:η^1 coordination mode to protect the overall hetero metallic co re.Due to the unique d-d transitions of Cu^Ⅱion,the reflectance spectrum of 1 displays broad and strong absorption towards visible light extending to the near-infrared region.Moreover,1 shows almost purely paramagnetic behavior with the presence of weak antiferromagnetic interactions at low temperatures. 相似文献