一类新奇的14电子构型,高价态,高活性单氧基（OXO）铼络合物

本文介绍近年来国外金属有机化学家报道的烷基及芳基三氧合铼（１４ｅ，Ⅶ）络合物ＲＲｅＯ３的合成和反应，以及利用该类络合物催化的烯烃歧化、烯烃环氧化和醛与重氮化合物烯烃化反应。     

四核稀土过氧根络合物吸收光谱的研究

本文介绍测定四核稀土过氧根络合物Ln_4O_4Cl_8(THF)_m(H_2O)_n(Ln=Pr、Nd,m+n=10)的紫外可见吸收光谱,归属处理光谱吸收峰。探讨了络合物在不同溶剂中的可能构型。初步结果表明,在非水溶剂中,四核稀土过氧根络合物能保持其稳定的四核核心构型Ln_4O_4Cl_4,随着体系中水含量的增加,四核络合物逐渐离解成单核络合物。文中还分析了促使四核络合物的离解因素。     

α-氨基酸乙酯卤根合铂(II)的合成和构型研究

Sixteen new halogenoethylaminoacidato Pt(II) complexes were synthesized and characterized, of which eightiodo complexes (PtA2I2) (A = DL-a-AlaOEt, L-a-alaOEt, DL-a-PheOEt, L-a-PheOEt, DI-A-AspOEt, L-a-AspOEt, DL-a-SerOEt and L-a-Lys OEt), four chloro compounds (PtA2Cl2)(A = DL-a-PheOEt, DL-a-AspOEt, L-a-Asp OEt) and (DL-a-PheHOEt)2(PtCl4) were obtained by reaction of K2 (PtX4)(X = I^-, Cl^-) with the corresponding ethylaminoacidates in water. The other chlorethylaminoacidato Pt(II) complexes (PtA2Cl2) (A = DL-a-AlaOEt, L-a-AlaOEt, L-a-PheOEt, DL-a-Ser OEt) were synthesized in acetone by exchange reaction of the corresponding iodo complexes with AgCl in order to avoid hydrolysis of the ethyl aminoacidates. Molar conductivity determination showed that all the Pt(II) complexes obtained were neutral molecules with the exception of (DL-a-PheHOEt)2(PtCl4) which existed as an anion. As shown by diole moment determination and modified thiourea reaction, iodo complexes 1-7 and some of the chloro complexes (PtA2Cl2) (A = DL-a-alaOEt, D-a-AlaOEt, DL-a-SerOEt) were of cis-configuration and the other chloro complexes were of trans-configuration.     

Mg和Ca-PDTA金属络合物分子内过程的DNMR谱

~1H NMR不但可以研究有机化学、金属有机化合物的立体结构,而且在某些适当的金属络合物体系中,还可以研究金属离子和配体间的迁移性及分子内过程的动力学。对于EDTA类金属络合物的DNMR研究表明分子内过程包括三种形式,即Δ≒Λ构型转化,N原子反转以及所谓的B≒R转化。本文作者为进一步探讨分子内过程,选PDTA为配体进行了DNMR研究,取得一些有意义的新结果。实验部分     

吡咯基金属络合物的制备及其在有机合成中的应用

本文综述了近年来吡咯基金属络合物的研究进展, 详细讨论了σ~N-、σ~C-、π-型吡咯基金属络合物的制备方法, 以及各类吡咯基金属络合物在有机合成中的应用。     

手性Salen-Ni(Ⅱ)络合物的ECD光谱及其绝对构型关联:可见区第一ECD吸收带的指纹作用

对系列手性salen-Ni(Ⅱ)络合物的电子圆二色(ECD)光谱及其绝对构型关联进行了概述.根据晶体结构和对固、液ECD光谱的表征,结合理论计算,着重探讨了准平面型手性[Ni(salen)]的固态结构及其在溶液中的绝对构型和优势构象.在此基础上通过若干实例说明了平面四方形[M(salen)]络合物两种绝对构型命名法,并给出了我们的建议.对[Ni(sal-R, R-chxn)] [sal-R, R-chxn = (R, R)-N, N'-双(亚水杨基)-1, 2-二亚氨基环己烷]的二氯甲烷溶液ECD光谱的计算结果表明,可见区第一个ECD吸收带主要是π →d荷移跃迁(LMCT)所致,而不是通常认为的d-d跃迁: [Ni(sal-R, R-chxn)]的绝对构型为Λ,其在可见区第一个ECD吸收带为正.将此ECD指纹应用于具有“闭壳层”电子结构的其它平面型手性[Ni(salen)]和六配位trans-[Co^Ⅲ(salen)L₂]络合物的绝对构型指认,具有一定的普适性.本文的研究结果对于深入理解手性[M(salen)]络合物的配位立体化学、手征光学性质及其手性识别和不对称催化机理具有重要科学意义.     

高氧化态(II-IV)三核金属簇合物构型分布的模式识别对应分析

本文采用模式识别方法, 对高氧化态(II-IV)三核簇合物的构型分布进行了对应分析, 找出了一组分类关系式, 为预报未知簇合物构型提供了定量的判据, 并初步讨论了构型分布和结构规律。     

高氧化态(II-IV)三核金属簇合物构型分布的模式识别对应分析

本文采用模式识别方法, 对高氧化态(II-IV)三核簇合物的构型分布进行了对应分析, 找出了一组分类关系式, 为预报未知簇合物构型提供了定量的判据, 并初步讨论了构型分布和结构规律。     

痂囊腔菌素A分子构型和分子内氢键的理论研究

用半经验量子化学AM1方法对天然苝醌化合物痂囊腔菌素A(EA)的分子构型和分子内氢键进行了研究;从EA可能的64种构型中选择16种进行了计算.结果表明,EA的X射线晶体结构对应的构型是II型左旋(A)a,a型(II-L-A-a,a);小的生成热差值可以使得异构体间的转换容易进行,有利于发生分子内质子传递.尽管采用AM1方法计算得到的EA各种构象的平面性有所差别,但都很接近晶体的平面性.此外,EA分子内氢键键能的平均值为22.9kJ/mol;II型的氢键键能比I型的大,(9,10)位的氢键键能比(3,4)位的大;EA的平面性是由苝醌环上的侧链取代所决定,而与分子内是否存在氢键无关.     

几种过渡金属混配配合物的构型和量子化学研究

对几种五配位的过渡金属配合物晶体结构构型进行了详细讨论,通过扭曲角的计算证明它们均为正三角双锥(TBP)和正向四方锥(TP)的过渡构型。运用AM1量子化学计算方法,对混配体的一些物理化学参数,特别是配位N原子轨道对前线轨道的贡献进行了研究。结果表明,配位N原子轨道对前线轨道的贡献不大,而且也不影响配位构型的变化。计算还表明大多数以三(2-苯并咪唑亚甲基)胺为配体的过渡金属配合物均具有扭曲的三角双锥构型,而铜配合物的构型随协同配体的不同,在正三角双锥和正向四方锥之间的变化范围很大,这是由于铜离子较强的John-Teller效应造成的。     

配位化学中新型金属配合物的电子结构与成键特点

研究配合物的几何电子构型、阐明配位键的本质是配位化学中重要的理论组成部分。本文在回顾配位化学基本的成键理论基础上,介绍几例近年来具有教科书级别的国内高水平原创工作,重点阐述具有独特芳香性、低氧化态、高配位数以及锕系金属的新型金属配合物的电子结构和成键特点,对丰富和拓展配位化学的基本理论具有重要意义。     

Unsymmetrical Sandwich Diphthalocyanine and Similar Complexes

Data on the synthesis and spectral and physicochemical properties of unsymmetrical sandwich diphathalocyanine and similar complexes are presented.     

Alkaline-Earth Metal Complexes with Pivaloylacetone

Pivaloylacetonates of alkaline-earth elements with composition M(Pa)₂ · nH₂O (n = 1, M = Sr, Ca; n = 0, 2, M = Ba) were synthesized and studied by IR and thermal analysis; their solubilities and volatility were estimated. It was found that the volatility changes regularly in the series M(Acac)₂–M(Pa)₂–M(Thd)₂ (HAcac is acetylacetone, HThd is dipivaloylmethane). The replacement of one methyl radical by the tert-butyl radical when going from acetylacetonates to pivaloylacetonates was shown to noticeably increase the volatility only for Sr(Pa)₂ · H₂O. Complexes of barium pivaloylacetonate with tetraglyme and -phenanthroline were synthesized and characterized.     

Gel Chromatographic Behavior of Labile Metal Complexes Trimeta- And Tetrametaphosphate Complexes with Bivalent Metal Cations

Abstract

The gel chromatographic behavior of metal ions in a labile complex formation system was expressed as a function of the ligand concentration in an eluent and the stability constants of the complexes. Trimeta- and tetrametaphosphate complexes with bivalent metal ions were used as examples. The retention volumes of the metal complexes were found to be always greater than those of the corresponding free ligands.     

Calixarene Complexes with Transition Metal Ions

Selected calixarene complexes with transition metal ions are described showing their syntheses and possible applications, especially in the aspect of the environmental protection.This revised version was published online in July 2005 with a corrected issue number.     

Transition Metal Complexes with Pyrazole Based Ligands

The complex formation of cobalt(II)-, nickel(II) and copper(II) sulphate hydrates with 3,5-dimethyl-1-thiocarboxamidepyrazole (HL) was studied. The influence of the anions on the course of the reaction was also examined, using nickel(II) salts with various anions. Beside the NiSO₄·7H₂O the reaction has been carried out with Ni(OAc)₂, Ni(CF₃COO)₂ and Ni(SCN)₂. Compounds with the following composition were obtained: Co(L)₃, Ni(L)₂ and [Cu(SCN)L]₂. The structure of the ligand and the Co(L)₃ complex was determined by single crystal X-ray analysis, while that of the Ni(L)₂ was solved by analysis of powder diffraction X-ray data. The most probable structure of the copper(II) complex is proposed on the basis of the elemental analyses data, FT-IR spectrometry and magnetic measurement. The thermal decomposition of the complexes was investigated by thermogravimetry, DSC and coupled TG-MS measurements. In the case of the nickel(II) compound, a relatively stable intermediate was detected in the 550-650 K temperature range. The composition of the intermediate, Ni(SCN)(NCS), was determined by FT-IR-spectrometry. This revised version was published online in July 2006 with corrections to the Cover Date.     

Complexes with a Metal Phosphorus Triple Bond

Herein we report the synthesis of different phosphido-complexes and -intermediates with WLE-triple bond. These compounds reveal different reactivity patterns. Details of reactivity as well as spectroscopic and theoretical aspects will be discussed in detail.     

过渡金属与华法灵配合物的合成和抗凝血作用研究

用过渡金属硝酸盐与华法灵钠在不同介质制备了金属配合物, 所试验的各种制备方法均可获得恒定组成的配合物NanML3•2H2O (L＝华法灵离子, n＝0, 1). 通过元素分析、红外光谱、摩尔电导、紫外光谱、热重和溶解性试验对配合物进行了表征. 抗凝血试验表明过渡金属华法灵配合物具有一定的抗凝血性质. 并对过渡金属华法灵、过渡金属水杨酸、稀土金属华法灵、稀土金属华法灵水杨酸配合物的抗凝血性质进行了比较.