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121.
Z. S. Klemenkova B. V. Lokshin L. I. Strunkina M. Kh. Minacheva 《Russian Chemical Bulletin》1994,43(9):1516-1521
Raman and IR spectra (4000-50 cm–1) of solid cyclopentadienyl zirconium and hafnium hydrides Cp2MH2, Cp2MD2, Cp2Zr(H)X, and Cp2Zr(D)X (Cp = 5-C5H5; M = Zr, Hf; X = Cl, Br) have been studied. The vibrational modes of MH groups, Cp-rings, and metal-ligand bonds are discussed and the band assignments are proposed. In the solid state, these complexes form polymers with linear hydride bridges of the M-H-M type. The force constants of the M-H and M-Cp bonds increase on going from Zr to Hf.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1604–1609, September, 1994. 相似文献
122.
设计合成了两种新型的以聚类吡唑硼酸盐为配体的钒氧配合物VO(acac)[HB(pz)3](1)和VO(acac)[HB(3,5-Me2pz)3]·CH3CN(2). 运用元素分析、 红外光谱和紫外光谱对所合成的配合物进行了表征, 并用X射线衍射测定了它们的晶体结构. 同时, 采用量子化学的Hartree Fock方法和自然轨道分析方法(NBO), 使用3-21G*(6d, 7f)基组计算得到了两个分子体系的分子轨道、原子电荷以及键级, 并对其结构进行了分析. 相似文献
123.
低氧条件下,钴(Ⅲ)的氮芥配合物具有合适的还原电位,就可能还原得到比较活泼的Co(Ⅱ)配合物,在溶液中其活性配体很快被体内的小分子取代,释放出的活性配体可以杀死低氧区内外的癌细胞,因此筛选合适的钴配合物作为低氧选择性抗癌药物的研究很有意义。本文以双 (2 氯乙基)胺(简称BCA)为活性配体,取代乙酰丙酮为辅助配体,合成一系列Co(Ⅲ)配合物(下图)。初步评估结果表明,其中两个配合物具有一定的低氧选择性,配合物的还原电位对药物的低氧选择性影响很大,合适的还原范围可能比较窄。1 实验部分1.1 试剂与仪器按文献[1]的方法合成… 相似文献
124.
[Co(amp)2Cl2]2[ZnCl4]体系中两对称异构体的2D NMR研究 总被引:7,自引:0,他引:7
The two symmetrical isomers in [Co(amp)2Cl2]2[ZnCl4](amp=2-(Aminomethyl)pyridine) system were syn-thesized by general oxidation method and were separated by chromatography and recrystallization method. Their configurations were assigned by using 2D NMR techniques, particularly the NOESY NMR spectra. Solvent used was Me2SO-d6 with the central peak of the CD3 septet as the reference ( 13C,δ 39.37; 1H,δ 2.49 relative to SiMe4). Cation exchange media used was Dowex 50Wx 2(H+ form, 200~400mesh; Biorad). 相似文献
125.
Fatma M. Abdel-Gawad Yousry M. Issa Hussein M. Fahmy Hanan M. Hussein 《Mikrochimica acta》1998,130(1-2):35-40
Three simple, quick and sensitive spectrophotometric methods are described for the determination of ciprofloxacin. The methods are based on the reaction of this drug as ann-electron donor with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), 7,7,8,8,-tetracyanoquinodimethane (TCNQ) andp-chloranil (CL) as -acceptors to give highly coloured complex species. The coloured products are quantitated spectrophotometrically at 460, 843 and 550 nm for DDQ, TCNQ and CL, respectively. Optimization of the different experimental conditions is described. Beer's law is obeyed in the concentration ranges 5–50, 1.5–15 and 20–200 g ml–1 ciprofloxacin, but the concentration ranges for best accuracy are 10–48, 2.5–15 and 35– 195 g ml–1 of drug for DDQ, TCNQ and CL, respectively. The relative standard deviations are less than 1.5%. Applications of the suggested methods to ciprofloxacin tablets are presented and compared with the USP method. The stability constants of the 11 DDQ and CL complexes were 1.086 × 104 and 2.581 × 104 lmol–1, respectively, whereas for the 12 TCNQ complex it was 3.62 × 1081. mol–1. 相似文献
126.
手性奎宁-卟啉锰催化剂的合成及其催化性能 总被引:1,自引:0,他引:1
为了寻找催化活性、相转移活性和手性诱导为一体的卟啉配体[1-4],我们把卟啉和手性相转移源连结起来,用奎宁-卟啉化合物作配体[5],考察其锰 配合物为催化剂对烯烃环氧化反应的催化性能。奎宁-卟啉锰 配合物结构式如下:1 实验部分1.1 试剂和仪器苯乙烯和α-甲基苯乙烯在氮气保护下减压蒸馏处理。氧源NaOCl的浓度由碘量法测定。其余试剂均为化学纯,色谱标样环氧苯乙烯和α-甲基环氧苯乙烯按文献[6]方法合成。奎宁-卟啉配体按文献[5]合成。260-50型红外光谱仪,KBr压片;UV-3000型紫外可见光谱仪,溶剂DMF;MT-3型CHN元素… 相似文献
127.
Polynuclear Complexes with Fe? As, Fe? Sb, and Fe? Bi Frameworks The anionic iron clusters Fe3(CO)112? and Fe4(CO)132? were reacted with compounds EX3 and with organic derivatives REX2 and R2EX of the elements arsenic, antimony, and bismuth. Commonly redox and cluster degradation reactions were observed. The new complexes [(CO)4Fe? AsMe2? Fe(CO)4]?, [HFe3(CO)9(mu;3-SbBut)]?, [Fe3(CO)10 (mu;3-Sb)]?, and [Fe3(CO)10(mu;3-Bi)]? were formed and isolated as their PPN salts. The Fe? As? Fe complex was identified by a structure determination, the other complexes were identified by their spectra. 相似文献
128.
129.
Yoshihiko Nishimori Katsuhiko Kanaizuka Dr. Masaki Murata Dr. Hiroshi Nishihara Prof. 《化学:亚洲杂志》2007,2(3):367-376
Films of linear and branched oligomer wires of Fe(tpy)2 (tpy=2,2′:6′,2′′‐terpyridine) were constructed on a gold‐electrode surface by the interfacial stepwise coordination method, in which a surface‐anchoring ligand, (tpy? C6H4N?NC6H4? S)2 ( 1 ), two bridging ligands, 1,4‐(tpy)2C6H4 ( 3 ) and 1,3,5‐(C?C? tpy)3C6H3 ( 4 ), and metal ions were used. The quantitative complexation of the ligands and FeII ions was monitored by electrochemical measurements in up to eight complexation cycles for linear oligomers of 3 and in up to four cycles for branched oligomers of 4 . STM observation of branched oligomers at low surface coverage showed an even distribution of nanodots of uniform size and shape, which suggests the quantitative formation of dendritic structures. The electron‐transport mechanism and kinetics for the redox reaction of the films of linear and branched oligomer wires were analyzed by potential‐step chronoamperometry (PSCA). The unique current‐versus‐time behavior observed under all conditions indicates that electron conduction occurs not by diffusional motion but by successive electron hopping between neighboring redox sites within a molecular wire. Redox conduction in a single molecular wire in a redox‐polymer film has not been reported previously. The analysis provided the rate constant for electron transfer between the electrode and the nearest redox‐complex moiety, k1 (s?1), as well as that for intrawire electron transfer between neighboring redox‐complex moieties, k2 (cm2 mol?1 s?1). The strong effect of the electrolyte concentration on both k1 and k2 indicates that the counterion motion limits the electron‐hopping rate at lower electrolyte concentrations. Analysis of the dependence of k1 and k2 on the potential gave intrinsic kinetic parameters without overpotential effects: k10=110 s?1, k20=2.6×1012 cm2 mol?1 s?1 for [n Fe 3 ], and k10=100 s?1, k20=4.1×1011 cm2 mol?1 s?1 for [n Fe 4 ] (n=number of complexation cycles). 相似文献
130.
钯(Ⅱ)-芳香氮碱-氨基酸三元配合物中的电子效应和芳环堆积作用 总被引:3,自引:0,他引:3
用pH-电位滴定法测定了Pd(L)(Aa)+三元配合物及相应的二元配合物,在25±0.5℃,30%的乙醇水溶液(体积分数),I=0.1(KNO3)条件下的稳定常数及表征常数。其中L=邻菲罗啉(phen)、苯并咪唑邻菲罗啉(PIP)、邻菲罗啉-5,6-二酮(dophen)、2,9-二甲基邻菲罗啉(dmphen)和联吡啶3,3′-二羧酸(BDA);Aa为甘氨酸(gly)、苯丙氨酸(phe)、酪氨酸(tyr)、S-苄基-半胱氨酸(bcys)、谷氨酰胺(glu)和γ-谷氨酰-α-萘胺(gnapa)。从配合物配体间的电子效应和芳环堆积等观点对配合物的附加稳定性进行了讨论,并计算了电子效应和芳环堆积效应各自对三元配合物附加稳定性的贡献。 相似文献