[C5H5Fe(CO)2]LnCl2·nTHF和[C5H5Fe(CO)2][C5H4(SiMe3)]LnCl·nTHF双核配合物的合成

合成了稀土铁双核配合物:(C₅H₅Fe(CO)₂)LnCl₂·nTHF(Ln=Nd,Sm,Gd;n=1,2)和(C₅H₅Fe(CO)₂)(C₅H₄(SiMe₃))·LnCl·nTHF(Ln=Nd,Sm,Gd;n=0,1,2)。元素分析,热分析,红外光谱和质谱分析确认了这两种配合物。红外光谱数据表明铁与稀土原子是以羰基桥连接。晶体结构分析表明((C₅H₅Fe(CO)₂)Na·4THF是(C₅H₅Fe(CO)₂)LnCl₂·nTHF合成的中间体。     

[C_5H_5Fe(CO)_2]LnCl_2·nTHF和[C_5H_5Fe(CO)_2][C_5H_4(SiMe_3)]LnCl·nTHF双核配合物的合成

合成了稀土铁双核配合物:〔C_5H_5Fe(CO)_2〕LnCl_2·nTHF(Ln=Nd,Sm,Gd;n=1,2)和〔C_5H_5Fe(CO)_2〕〔C_5H_4(SiMe_3)〕·LnCl·nTHF(Ln=Nd,Sm,Gd;n=0,1,2)。元素分析,热分析,红外光谱和质谱分析确认了这两种配合物。红外光谱数据表明铁与稀土原子是以羰基桥连接。晶体结构分析表明〔(C_5H_5Fe(CO)_2〕Na·4THF是〔C_5H_5Fe(CO)_2〕LnCl_2·nTHF合成的中间体。     

[(CO)2(C5H5)Fe]2C60的合成与表征

有关 C6 0 取代的金属羰基化合物的研究方兴未艾 .C6 0 作为一个特殊的烯烃 ,以六元环间的碳碳双键提供电子对 ,与过渡金属羰基化合物形成诸如 η2 ,η4 ,η6等结构新颖的化合物约有 40多例 [1～ 5] ,但只有一例是以 Fe为中心原子的 C6 0 取代的金属羰基化合物 ( η2 - C6 0 ) Fe( CO) 4 [1] .本文报道了第一例 C6 0配位的 Fe的双核金属羰基化合物 [( CO) 2 ( C5H5) Fe]2 (η2 - C6 0 ) ,并通过元素分析 ,IR,1H NMR,13CNMR和 XPS进行表征 .1　实验部分[Fe( CO) 2 ( C5H5) ]2 购自 Aldrich公司 .C6 0 纯度为 99% .其余试剂均…     

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-C_5H_4PhMeSiSiMePh-C_5H_4]Fe_2(CO)_2(μ-CO)_2(1)was synthesized by a modified procedure,from which the trans-isomer 1b that was pre-viously difficult to obtain has been isolated for the first time.More interestingly,two new regio-isomers[η~5,η~5C_5H_4SiMe(SiMePh_2)C_5H_4]Fe_2(CO)_2(μ-CO)_2(2)and [η~5,η~5-C_5H_4Me_2SiSiPh_2C_5H_4]Fe_2(CO)_2(μ-CO)_2(3)were occa-sionally obtained during above process,the novel structures of which opened up new options for further study ofthis type of Si—Si bond-containing transition metal complexes.The molecular structure of 2 has been determinedby the X-ray diffraction method.     

环状配合物Me_2Si［η~5－C_5H_4Fe（CO）_2］_2SnR_2的合

通过ＳｎＣｌ_２对化合物Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）］_２（μ－ＣＯ）_２（Ⅰ）中Ｆｅ－Ｆｅ键的插入反应以及Ⅰ被Ｎａ－Ｈｇ齐还原所生成的相应双铁负离子｛Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）_２］_２｝~（２－）与ＳｎＲ_２Ｃｌ_２（Ｒ＝Ｍｅ，Ｐｈ）的亲核反应，合成了环状化合物Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）_２］_２ＳｎＲ_２［Ｒ＝Ｃｌ（１），Ｍｅ（２），Ｐｈ（３）］。以元素分析、ＩＲ和~１ＨＮＭＲ谱表征了它们的结构，并用Ｘ射线衍射测定了配合物３的晶体结构。３为单斜晶系，空间群Ｐ２_１／ｎ，ａ＝１．０３８４（３）ｎｍ，ｂ＝１．６３８４（１）ｎｍ，ｃ＝１．５７６２（５）ｎｍ，β＝９７．９３（２）°，Ｖ＝２．６５６（２）ｎｍ~３，Ｚ＝４，Ｄｘ＝１．７１ｇ／ｍＬ。     

[Cp_2Ti(L)X]的ESR谱研究

本文研究了配合物[Cp_2Ti(L)X](Cp:C_5H_5,Me~-C_5H_4,C_5Me_5;L:瞵、异腈、吡啶、胺、一氧化碳等;X:F,Cl,Br,I)的ESR谱,获得了这些配合物的波谱参数。发现在Cl,Br,I三个系列中,g值与钛超精细偶合常数a(Ti)值随L的变化呈线性关系。观测到大量g>g_e的Ti(Ⅲ)配合物的ESR谱,对其规律性进行了探讨。     

簇合物[Fe2(CO)8]2-和[Fe3S(CO)9]2-成簇类型的光谱探讨及电子光谱和电子结构研究

在Fe(CO)₅+[Et₄N]₂MoS₄相同体系中,改变原料配比及碱度,可得到3种簇合物:(Ⅰ)[Et₄N]₂[Fe₂(CO)₈]、(Ⅱ)[Et₄N]₂[Fe₃S(CO)₉]、(Ⅲ)[Et₄N]₃[FeMo₂S₈O₂]。本文用电子光谱法考察了各簇合物的生成条件。根据X光结构分析,用群分解的EHMO程序,计算了(Ⅰ)、(Ⅱ)簇合物阴离子骨架能级,并研究了它们的电子光谱及电子结构。     

配合物{[(C9H7)3Yb]2Cl}[Na·6THF] (Ⅰ)的合成及其还原生成(C9H7)2Yb·2THF (Ⅱ)的研究、配合物I和II的晶体结构

三氯化钇与茚基钠以1∶2摩尔比于THF中,在50 ℃下反应,歧化生成了离子型配合物[(C9H7)3Yb]2Cl[Na·6THF] (Ⅰ). X射线结构分析表明,配合物Ⅰ是由阴离子{[(C9H7)3Yb]2Cl}-及阳离子[Na·6THF] 组成的离子对,阴离子由一个氯桥把两个(C9H7)3Yb基团连接在一起.配合物[(C9H7)3Yb)2Cl][Na·6THF]为三斜晶系,P1空间群,晶胞参数,a=1.0682(2) nm, b=1.2687(3) nm, c=1.2869(2) nm,α=87.223(1)°, β=81.755°, γ=88.217°, V=1.7273(1) nm3, Z=1.配合物I的结构用重原子法确定,用full-matrix least-squares法修正,一致性因子为 R=0.062, Rw=0.072.配合物{[(C9H7)3Yb]2Cl}[Na·6THF]与金属钠反应,生成(C9H7)2Yb·2THF (Ⅱ).配合物Ⅱ的分子结构经过了X射线的表证.     

Some Regularities of Standard Enthalpies of Formation (SEF) for Relative Inorganic Compounds

The empirical regularities of the SEF for relative inorganic substances in binary and quasibinary systems (energetic and dimensional rules of linear approximation - ELAR and DLAR) are described. This revised version was published online in August 2006 with corrections to the Cover Date.     

Bonding analysis and the mechanisms on the ring-opening of alkoxy-bridged bis(silylene) transition-metal complexes toward MeOH

The mechanistic study on the ring-opening of alkoxy-bridged bis(silylene) transition-metal complexes toward MeOH is performed by using density functional theory. Four steps are predicted to be involved in the reaction, formation of hydrogen bonding between R and a MeOH, ring-opening of the Ru-Si1-O1-Si2 four-membered ring, formation of the six-membered ring, and the hydroxyl hydrogen migration to the metal center. It is found that the reaction is favorable thermodynamically and the hydroxyl hydrogen migration is the rate-determining step. Systematic variations of the structural parameters involved in the reaction mechanism are revealed, which revealed the relationship of the bond strength among Ru-Si, Si-O and O-H bonds.     

Copper(I) bromide and chloride complexes with urotropine and triethylenediamine: synthesis,crystal structure,and Raman characterization*

Abstract

In the present study, the oxidative dissolution of metallic copper has been explored with the intention to prepare some new complexes with urotropine (hmta) and triethylenediamine (dabco) ligands. All the compounds synthesized were characterized by single-crystal X-ray diffraction and Raman spectroscopy. Reactions performed in a DMSO/CuCl₂?2H₂O mixture resulted in [(μ-Cl)₂Cu^I(hdabco⁺)Cu^I(μ-Cl)(κS-DMSO)]_n and [Cu^ICl(hmta)₂] complexes. Their isostructural bromide analogs [(μ-Br)₂Cu^I(hdabco⁺)Cu^I(μ-Br)(κS-DMSO)]_n and [Cu^IBr(hmta)₂] were prepared by the reaction of elemental copper with respective ligands in a DMSO/CBr₄ mixture. Early interrupted reaction of the copper wire with the DMSO/CBr₄/dabco solution resulted in an appearance of crystals of the [Cu^I₂Br₂(CO)₂(dabco)]_n carbonyl complex on the copper surface. It arises with the participation of in situ formed carbon monoxide. Despite the identical stoichiometry, the crystal structure of the [Cu₂Br₂(CO)₂(dabco)]_n complex is markedly different from that of a known [Cu₂Cl₂(CO)₂(dabco)]_n analog.     

Die Kristallstrukturen der Vanadium-Weberite Na2MIIVIIIF7 (MII  Mn,Ni, Cu) und von NaVF4

The Crystal Structures of the Vanadium Weberites Na₂M^IIV^IIIF₇ (M^II ? Mn, Ni, Cu) and of NaVF₄ At single crystals of the vanadium(III) compounds NaVF₄ (a = 790.1, b = 531.7, c = 754.0 pm, β = 101.7°; P2₁/c, Z = 4), Na₂NiVF₇ (a = 726.0, b = 1031.9, c = 744.6 pm; Imma, Z = 4) and Na₂CuVF₇ (a = 717.6, b = 1043.5, c = 754.6 pm; Pmnb, Z = 4) X-ray structure determinations were performed, at Na₂MnVF₇ (a = 746.7, c = 1821.6 pm; P3₂21, Z = 6) a new refinement. NaVF₄ crystallizes in the layer structure type of NaNbO₂F₂. The fluorides Na₂M^IIVF₇ represent new orthorhombic (M^II ? Ni; Cu) resp. trigonal (M^II ? Mn) weberites. The average distances within the [VF₆] octahedra of the four compounds are in good agreement with each other and with data of related fluorides (V? F: 193.3 pm). The differences between mean bond lengths of terminal and bridging F ligands are 5% in NaVF₄, but less than 1% in the weberites. Details and data for comparison are discussed.     

A Tetranuclear Zinc(II) Complex of a [4+4] Macrocyclic Schiff Base Ligand

The cyclocondensation reaction between sodium 2,6-diformyl-4-methylphenolate(sdmp) and 1,5-diamino-3-(1-hydroxyethyl)azapentane (dhap) followed by in situ transmetallation with Zn(ClO₄)₂6H₂O produced a tetranuclear zinc(II)complex of the current biggest-sized [4+4] Schiff base macrocyclic ligand. The structure of the complex has been determined by X-ray techniques, indicating that the hydroxyethyl group of the amine, dhap, has been eliminated in the process. For comparison, the reaction of sdmp with diethylenetriamine has also been carried out. The resulting product has been characterized by its infrared and positive ion FAB mass spectra, which turned out to be a mixture of the corresponding [3+3] and [4+4] macrocyclic Schiff bases together with thecommon [2+2] mode.     

（Et4N）m.M（dmit）2型配合物的合成及其红外光谱

（Ｅｔ_４Ｎ）_ｍ·Ｍ（ｄｍｉｔ）_２型配合物的合成及其红外光谱李洪启,王爱勤,宋燕西,谭干祖,姚钟麒,俞贤达（中国科学院兰州化学物理研究所兰州７３００００）关键词二（二硫杂环戊烯硫酮二巯基）金属,配合物,合成,红外光谱由二（１,３－二硫杂环戊烯－２－...     

The effect of titanium alkoxides in the synthesis of heterobimetallic complexes by titanocene(III) alkoxide-induced metal-metal bond cleavage of metal carbonyl dimers

A series of titanocene(III) alkoxides L₂Ti(III)OR where L = Cp, R = Et(1b), ^tBu(1a), 2,6-Me₂C₆H₃(1c), 2,6-^tBu₂-4-Me-C₆H₂(1d), or L = Cp*, R = Me(2e), ^tBu(2a), Ph(2f) was synthesized and subjected to reaction with [CpM(CO)₃]₂ [M = Mo, W], [CpRu(CO)₂]₂, and Co₂(CO)₈. The Ti(III) precursors 1a, 1c, 2a, 2e, and 2f reacted with [CpM(CO)₃]₂ [M = Mo, W] to form heterobimetallic complexes L₂Ti(OR)(μ-OC)(CO)₂MCp [M = Mo, W], of which Ti and M are linked by an isocarbonyl bridge. Reactions of these Ti(III) complexes with Co₂(CO)₈ resulted in formation of Ti-Co₁ heterobimetallic complexes, from 2a, 2e, or 2f, or Ti-Co₃ tetrametallic complexes, Cp₂Ti(O^tBu)(μ-OC)Co₃(CO)₉ from 1a, 1b, or 1c. The products were characterized by NMR, IR, and X-ray crystallography. Reaction mechanisms were proposed from these results, in particular, from steric/electronic effects of titanium alkoxides.     

Rapid and Convenient Method for the Determination of Sodium Nitroprusside in Aqueous Solution

Abstract

We propose a rapid and convenient method for the determination of sodium nitroprusside in aqueous solution. In alkaline medium and in the presence of dimethylsulfoxide, the concentration of the nitrite ions coming from the nitroprusside corresponds with the initial quantity of this compound.     

脉冲辐解法研究大环二氧四胺铜(Ⅱ)配合物歧化超氧离子的动力学

用脉冲辐解法研究大环二氧四胺配体的铜配合物12-(4'-硝基)-苄基-1,4,7,10-四氮杂环十三烷-11,13-二酮合铜(Ⅱ)歧化超氧离子的动力学,求得其歧化速率常数K_cat为1.78×10⁶mol^-1·L·s^-1(pH=7.0)和1.06×10⁶mol^-1·L·s^-1(pH=7.8)。其反应机理与超氧歧化酶有类似之处。