新型含硅表面活性剂的合成及性能研究

含有双胺基的三硅氧烷中的伯胺基与D-葡萄糖酸-δ-内酯进行酰胺化,仲胺基与低聚乙二醇甲醚缩水甘油醚、二缩水甘油醚进行烷基化,制备了新型含硅表面活性剂Me₃SiOSiMeR¹OSiMe₃ [R¹=(CH₂)₃NR²(CH₂)₂NHCO(CHOH)₄CH₂OH; R²=H, CH₂CH(OH)CH₂O(CH₂CH₂O)_xCH₃, x=1, 2, 3] (1a, 2a～2c)和(CH₂OCH₂)_y(Me₃SiOSiMeR³OSiMe₃)₂ [R³=(CH₂)₃NR⁴～(CH₂)₂NHCO(CHOH)₄CH₂OH; R⁴=CH₂CH(OH)CH₂OCH₂, y=0, 1, 2] (3a～3c).这些化合物的结构用¹H, ¹³C核磁共振仪和元素分析仪进行鉴定.研究了这些新型含硅表面活性剂的界面性能,在浓度分别为10^-4和10^-5 mol·L^-1时可以将水的表面张力降低至约21 mN·m^-1.     

Kishner-Wolff改良法——Ⅹ.邻芳族羟基羰基化合物的还原

研究了邻芳族羟基羰基化合物的Kishner-Wolff改良法还原,并讨论了它们的反应机制.萘酚系羰基化合物5与6中的R为H或C₆H₅(5a、6a、6b)时,还原后得高得率的正常还原物;如R为C₆H₅CH₂,C₆H₆CH₂CH₂(5b、5c、6c),则除得正常还原物外,还得含氮环化物;如R为CH₃、CH₃CH₂、CH₃CH₂CH₂、(CH₃)₂CH(5d～g),则同时得正常还原物及含氮环化物,增加R中碳原子数,似乎使正常还原物减少,而含氮环化物增加.当R为CH₃(CH₂)₆(5h),则仅得含氮环化物.苯酚系羰基化合物7中的R为烷烃基或芳族基时,均得高得率的正常还原物.     

NMR研究溶液中正十四烷基硫酸钠/正十四烷基聚氧乙烯醚(3)表面活性剂之间的相互作用

采用¹HNMR弛豫、自扩散系数和二维相敏(2DNOESY)实验研究了正十四烷基硫酸钠[n-CH₃(CH₂)₁₃OSO₃Na(STS)]和正十四烷基聚氧乙烯醚(3)[n-CH₃(CH₂)₁₃O(C₂H₄O)₃H(C₁₄E₃)]在溶液中的自聚集以及二者混合后的相互作用.结果表明,STS与C₁₄E₃混合后存在相互作用,并形成混合胶束;弛豫实验表明,混合胶束中STS疏水链质子运动更加受阻,C₁₄E₃的α-(4″)和β-CH₂(3″)处链堆积紧密.C₁₄E₃的亲水端(CH₂CH₂0)₃链卷曲紧贴在疏水壳表面外链堆积较紧密处.自扩散系数测量表明,混合胶束比单一阴离子表面活性剂形成的胶束大.单一非离子型胶束和混合胶束的亲水端(CH₂CH₂0)₃(5″)链构成相应较软和松散的外壳.单一C₁₄E₃在极性溶剂氯仿溶液中,质子运动比在水中自由度大,但2DNOESY谱中出现了少量分子间的交叉峰,也可能形成了一些小的聚集体.     

乙醇在Co(111)表面脱氢反应机理的第一性原理研究

采用密度泛函理论和周期平板模型相结合的方法针对Co（111）表面上乙醇脱氢反应的反应机理进行了细致的研究,同时,对反应过程中涉及到的各个物种在表面上不同吸附位（顶位（top）,桥位（bridge）,三重空穴位（fcc和hcp））的吸附模型进行了结构优化以及相关能量的计算,确定了各物种的最佳吸附位点.研究结果表明,CH₃CH₂OH在Co（111）表面的脱氢反应可具体描述为三条反应路径：反应路径I为CH₃CH₂OH逐步脱氢经由中间体CH₃CHO,最终生成CH₄和CO的反应;反应路径Ⅱ为CH₃CH₂OH脱氢产生的CH₃CH₂O基和CH₃CHO相互作用通过CH₃COOH分子最终生成CH₄和CO₂的反应;反应路径Ⅲ为CH₃CH₂O基和CH₃CO基作用生成CH₃COOC₂H₅的过程,其中,反应路径I为最优路径（CH₃CH₂OH→CH₃CH₂O→CH₃CHO→CH₃CO→CH₃+CO→CH₂→CH→CH₄+CO+C+H）,该反应路径中的CH₃CH₂O基脱氢生成CH₃CHO为速控步骤,反应能垒为1.61 eV.     

过渡金属甲基磺酸盐催化醇的四氢吡喃化反应

以过渡金属甲基磺酸盐［Mn(CH₃SO₃)₂·2H₂O, Cu(CH₃SO₃)₂·4H₂O, Co(CH₃SO₃)₂·4H₂O和Zn(CH₃SO₃)₂·4H₂O］为催化剂,在室温条件下催化醇的四氢吡喃化反应,并对反应条件进行了优化。结果表明：当醇用量为30 mmol,醇和3,4-二氢吡喃摩尔比为1.0 ：1.1,甲基磺酸盐用量为1 mmol,二氯甲烷20 mL时,可高效催化醇的四氢吡喃化反应。与路易斯酸催化活性相比,过渡金属甲基磺酸盐催化醇的四氢吡喃化反应效果最好,催化酚的效果较差。用Mn(CH₃SO₃)₂·2H₂O和Cu(CH₃SO₃)₂·4H₂O催化正丁醇的四氢吡喃化反应,重复使用5次,收率分别为89%和92%。     

层状钴有机膦酸化合物的合成以及变磁行为

从配体C₆H₅CH₂N(CH₂PO₃H₂)₂ (H₄L)出发, 在水热条件下得到了两个层状结构化合物Co₂(L)(H₂O)₂·0.3H₂O (1)和Co₂(L)(H₂O) (2). 在这两个化合物的层结构中分别存在“之”字型和“蝴蝶”型的{Co₄O₆}四核簇结构单元, 相邻四核通过O-P-O桥连形成二维无机层状结构, 有机基团位于层与层之间. 磁性测试表明, 化合物1中存在反铁磁耦合, 并且在低温下表现出场致变磁行为; 我们还对化合物1的脱水样品(1-de)进行了磁性测试, 测试结果表明化合物1-de存在自旋翻转现象. CCDC: 908112 (1), 908113 (2).     

分子自组装法制备具有可控浸润性的铜表面

通过简单浸泡的方法在铜基底上制备出了具有微纳米复合结构的氧化铜, 再利用混合硫醇溶液[含HS(CH₂)₉CH₃和 HS(CH₂)₁₁OH]对浸泡后的表面进行修饰, 通过控制溶液中HS(CH₂)₁₁OH的浓度, 制备出一系列具有不同浸润性的铜表面, 实现表面从超疏水到超亲水的有效调控. 研究发现, 表面浸润的可控性源于表面复合结构与不同化学组成的协同作用, 微纳米复合结构的存在为表面浸润性的调节提供了必要的条件.     

Nd(Ⅲ)与Hbbimp配合物的合成及其与DNA的作用研究

合成并表征了新的双核配合物[Nd₂(bbimp)(CH₃COO)(CH₃CH₂O)₂(CH₃CH₂OH)](ClO₄)₂,Hbbimp=2,6-二[二(2-苯并咪唑甲基)]氨甲基-4-甲基苯酚.用光谱学手段研究了配合物与小牛胸腺(CT)DNA的作用,结果表明,配合物使CT的DNA最大吸收峰发生减色和红移;使溴化乙锭(EB)-DNA复合物体系荧光强度减弱;热变性实验表明配合物使DNA的变性过程和降解过程共存.在50℃,pH=8.0时,单独的配合物对超螺旋质粒pBR322DNA的断裂的效果最好,可将大部分超螺旋DNA(CCC带)转化为缺刻产物(OC带);当c(H₂O₂)<1×10^-3mol/L,n(配合物):n(H₂O₂)=1:20时,配合物在较低浓度时即可将CCC带全部转化为OC带.     

γ-苄基膦酸-磷酸锆的合成、表征及插层性能研究

于220℃水热晶化下制备了高结晶度的γ-ZrP,合成了3种γ-苄基膦酸-磷酸锆层状化合物Zr(PO₄).(H₂PO₄)_0.15(C₆H₅CH₂PO₃H)_0.85·0.4H₂O(1,d=1.86nm),Zr(PO₄)(H₂PO₄)_0.30(C₆H₅CH₂PO₃H)_0.70·0.6H₂O(2,d=1.78nm)和Zr(PO₄)(H₂PO₄)_0.50(C₆H₅CH₂PO₃H)_0.50·0.7H₂O(3,d=1.66nm).用X射线粉末衍射和³¹P固态核磁共振等手段表征其结构,并研究了其与α-苯乙胺的插层性能.     

螯合型手性取代环戊二烯钛族络合物的结构研究

作者从分析二氯二茂钛及其它一些晶体结构出发,设计并合成了螯合型取代环戊二烯配体CH₃OCH₂CH₂CpH(1),用此制得了络合物(CH₃OCH₂CH₂Cp)₂TiCl₂(2),(CH₃OCH₂CH₂Cp)CpTiCl₂(3),测定了(2)和(CH₃OCH₂CH₂Cp)TiCl₃(4)的晶体结构,取得了配体形成螯合环的证据。用(2)/P_rⁱZMgBr进行1,5-己二烯催化异构化,得到了高转化率(99%)和高选择性(专一生成甲叉环戊环,90%)。     

Zum komplexchemischen Verhalten von potentiell vier- und fünfzähligen Bis(salicylidenamino)-Liganden gegenüber Ionen der 3d-Elemente

Studies on the Coordinative Behaviour of Potentially Four and Fivedentate Bis(salicylidene amino)-Ligands with Ions of the 3d-Elements. Fourdentate bis(salicylidene amino)-ligands (^?ONΦCH₂ΦNO^? and ^?ONΦOΦNO^?, meaning of the abbreviations see text) with the centres of donor atoms connected by rigid, bifunctional residues, form polymeric complexes Me^II(ONΦCH₂ΦNO) and Me^II(ONΦOΦNO) with cobalt(II), nickel(II), and copper(II). Among the cobalt(II) chelates the structure is uniformly tetrahedral, but the nickel(II) and copper(II) complexes contain square planar central atoms and such with a higher coordination number side by side. The potential fivedentate ligands ^～ON3PPh3NO^?, ^?ON2O2NO^?, and ^?ON2S2NO^? differ as to their coordinative behaviour. The coordination number of the complexes Ni(ON3PPh3NO) and Co(ON3PPh3NO) is five. On the other hand the compounds Co(ON2S2NO) and Co(ON2O2NO) are tetrahedral. No coordination of the ether or sulfide group is observed. Ni(ON2O2NO) has an octahedral structure which is produced by coordination polymerisation and possibly by coordination of the ether group. The new complexes are compared with the transition metal complexes of simple salicylaldimines.     

Darstellung und Eigenschaften löslicher und Polysiloxangebundener (Ether-Phosphan)ruthenium(II)-Komplexe

Preparation and Properties of Soluble and Polysiloxane-Supported (Ether-Phosphine)ruthenium(II) Complexes Phosphine-modified Polysiloxanes of the type x SiO₂ · [SiO_3/2(CH₂)₆P(Ph)R] (x = 0 – 3, I–IV ) were prepared by hydrolytic condensation of (MeO)₃Si(CH₂)₆P(Ph)R [ 1 ; R = CH₂CH₂OMe ( a ), CH₂C₄H₇O ( b ), CH₂C₄H₇O₂ ( c ), Ph ( d )]. Crosslinking was achieved by cocondensation of 1 and Si(OEt)₄. 2 SiO₂ · [SiO_3/2(CH₂)₆P(Ph)CH₂CH₂OMe] ( IIIa ) was investigated by means of ³¹P and ²⁹Si CP-MAS-NMR-spectroscopy, especially in view of a quantification of silyl species which revealed the following ratios: T₂:T₄:Q₂:Q₃:Q₄ = 76:158:48:135:82. Reaction of RuCl₂(PPh₃)₃ with 3 moles of 1a gave fluxional RuCl₂(P∩O)(P～O)₂ ( 4a ). From its temperature dependent ³¹P{¹H}-NMR spectrum the temperatures of coalescence and the corresponding activation enthalpies could be estimated at -25°C (46 kJ · mol^?1) and +20°C (55 kJ · mol^?1). Soluble 1a-d as well as their insoluble counterparts I-IV were treated with [RuCl₂(CO)₂]_n to give all-trans-RuCl₂(CO)₂(PR₃)₂ ( 6 ). On heating (120°C) 6 could be transformed into isomeric cis, cis, trans-RuCl₂(CO)₂(PR₃)₂ ( 7 ). Decarbonylation occurred on irradiation of 6 . Polysiloxane-supported ruthenium complexes were proved to be active in the heterogeneous hydrogenation of crotonaldehyde. Thus, at p(H₂) = 50 bat, T = 120°C, reaction time = 190 min, and at a molar ratio of aldehyde: Ru = 250:1, all-trans-RuCl₂(CO)₂(P～O)₂ ( 6f , O,P = IIIa ) effected a conversion of 50%, crotyl alcohol being formed in comparatively high selectivities. Moreover, no loss of metal or ligand from the support could be observed.     

Fabrication of lead titanate nanocrystals via gas-bubbling sol–gel process

With Pb(CH₃COO)₂ · 3H₂O and Ti(C₄H₉O)₄ as precursor materials, (CH₃)₂CHOH and ammonium tartrate as solvent and surfactant, respectively, the ferroelectric lead titanate (PT) nanocrystals of tailorable sizes were successfully prepared via a novel gas-bubbling sol–gel process, in which water and ammonia were carried into the solution by nitrogen gas through a bundle of stainless steel needle-like tubes, and a subsequent heating treatment in an oxygen-free atmosphere. It has been found that the dimensions of resulting nanocrystals are strongly affected by the internal diameter of tubes for gas-bubbling, while the velocity of carrier gas flowing in the tubes mainly controls the bubbling rate or the yield of nanocrystals. The possible mechanism for the formation of size-tailorable nanocrystals via such a gas-bubling sol–gel process is discussed in this paper.     

Crystallisation Solvent Influence on the Crystal Structures of MnII and NiII Complexes with 2,6‐bis(1‐salicyloylhydrazonoethyl)pyridine,H4daps

Neutral manganese and nickel complexes of the empirical formulae Mn(H₂daps)(H₂O)_0.5 and Ni(H₂daps) · (H₂O)_1.5(CH₃CN) have been prepared by electrochemical syntheses. The structures of the complexes formed from solvents with different donor ability were investigated. Recrystallisation of Mn(H₂daps)(H₂O)_0.5 from pyridine and ethanol yields [Mn(H₂daps)(py)₂] 1 and [Mn(H₂daps)(C₂H₅OH) · (H₂O)] 2 . Slow evaporation of dichloromethane and methanol solutions of Ni(H₂daps)(H₂O)_1.5(CH₃CN) allows the isolation of single crystals of [Ni₂(H₂daps)₂] · CH₂Cl₂ 4 and [Ni₂(H₂daps)₂(CH₃OH)₂] · 3 CH₃OH · H₂O 5 , suitable for X‐ray diffraction studies. Recrystallisation of 4 from pyridine yields [Ni₂(H₂daps)₂(py)₂] · CH₂Cl₂ 6 , previously characterised by us. This study shows the versatility of the H₄daps ligand and the influence that the crystallisation solvent can have on the crystal structure of these complexes.     

Homogeneous Catalytic Hydrogenation of Amides to Amines

Hydrogenation of amides in the presence of [Ru(acac)₃] (acacH=2,4‐pentanedione), triphos [1,1,1‐tris‐ (diphenylphosphinomethyl)ethane] and methanesulfonic acid (MSA) produces secondary and tertiary amines with selectivities as high as 93 % provided that there is at least one aromatic ring on N. The system is also active for the synthesis of primary amines. In an attempt to probe the role of MSA and the mechanism of the reaction, a range of methanesulfonato complexes has been prepared from [Ru(acac)₃], triphos and MSA, or from reactions of [RuX(OAc)(triphos)] (X=H or OAc) or [RuH₂(CO)(triphos)] with MSA. Crystallographically characterised complexes include: [Ru(OAc‐κ¹O)₂(H₂O)(triphos)], [Ru(OAc‐κ²O,O′)(CH₃SO₃‐κ¹O)(triphos)], [Ru(CH₃SO₃‐κ¹O)₂(H₂O)(triphos)] and [Ru₂(μ‐CH₃SO₃)₃(triphos)₂][CH₃SO₃], whereas other complexes, such as [Ru(OAc‐κ¹O)(OAc‐κ²O,O′)(triphos)], [Ru(CH₃SO₃‐κ¹O)(CH₃SO₃‐κ²O,O′)(triphos)], H[Ru(CH₃SO₃‐κ¹O)₃(triphos)], [RuH(CH₃SO₃‐κ¹O)(CO)(triphos)] and [RuH(CH₃SO₃‐κ²O,O′)(triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed.     

Synthesis,isomerization, and polymerization of mixed phosphoranimines

A series of phosphites were prepared bearing various combinations of phenoxy, methoxy, and trifluoroethoxy substituents. (PhO)₃P, (CF₃CH₂O)(PhO)₂P, (CF₃CH₂O)₂(PhO)P, and (CH₃OCH₂CH₂O)(PhO)₂P were polymerized during the course of the Staudinger reaction with azidotrimethylsilane to form low molecular weight polyphosphazenes. Similar reactions with (CH₃O)(CF₃CH₂O)₂P, (CH₃O)(PhO)₂P, (CH₃O)₂(CF₃CH₂O)P, (CH₃O)₂(PhO)P, and (CH₃O)₃P produced the desired phosphoranimine as well as the corresponding phosphoramidate isomer. Studies were performed on these systems in order to understand the nature of this isomerization. (CH₃O)(PhO)₂P (DOUBLE BOND) N (SINGLE BOND) Si(CH₃)₃ and (CH₃O)₂(PhO)P (DOUBLE BOND) N (SINGLE BOND) Si(CH₃)₃ polymerize at temperatures above 150°C. © 1996 John Wiley & Sons, Inc.     

Novel coordination behavior of a pteridine-benzoylhydrazone ligand (BZLMH): Theoretical calculations, XRD structures and luminescence studies

The XRD structure and the influence of the conformation in the molecular orbitals of the pteridine-benzoylhydrazone ligand (BZLMH = benzoylhydrazone of 6-acetyl-1,3,7-trimethyllumazine, lumazine = (1H,3H)-pteridin-2,4-dione) have been studied. Complexes of BZLMH with nickel(II), zinc(II) and mercury(II) have been prepared and spectroscopically characterized by IR, NMR and fluorescence spectroscopy; also XRD studies have allowed to establish two different coordinative patterns in the complexes [Ni₃(BZLMH)₃(OH)(H₂O)(CH₃CN)₂](ClO₄)₅ · 2H₂O · CH₃CN (2) and [Zn(NO₃)(BZLMH)(H₂O)](NO₃) (3). Compound (2) is a trinuclear hydroxo-centered complex with a central hydroxo group bridging the three nickel(II) ions. The [Ni₃(μ₃-OH)]⁵⁺ core is planar with the benzoylhydrazone ligands coordinated in the bis-bidentate [O(4),N(5)]-[N(61),O(63)] mode. The zinc(II) compound displays a BPT coordination geometry in which the BZLMH ligand acts in a tridentate fashion using N(5), N(61) and O(63) donor atoms. Fluorescence spectroscopic properties of benzoylhydrazone (BZLMH) are studied and the fluorescence band shift and changes in intensity is modulated by complexation with different metal ions (Ni²⁺, Zn²⁺ and Hg²⁺), so the binding is signaled such a possible cause.     

Metal complexes of mercaptoamines—III. Different behaviour of β- and γ-(N,N-dimethyl)-mercaptoamines

The complexes Ni₆(MPDMA)₁₂, [Ni₆(MPDMAH)₁₂]X₁₂ X = (I, ClO₄) and Pd₂(MPDMA)₂Cl₂ (MPDMA = ^t-S(CH₂)₃N(CH₃)₂) have been prepared and characterized. An X-ray diffraction study shows that the structure of [Ni₆(MPDMAH)₁₂] (ClO₄)₁₂ consists of a cyclic hexanuclear array of nickel atoms linked by sulphur bridging ligands. Infrared and electronic spectra show that there is no chelation in any of the nickel complexes. However, coordination through the nitrogen atoms occurs in the palladium complex. This behaviour differs from that of the homologous β-mercaptoamine, which forms monomeric chelate complexes with both nickel and palladium.     

Synthesis,spectroscopy and thermal analysis of nickel(II), palladium(II) and copper(II) complexes with N,N′-bis(2-hydroxyethyl)-oxamide

Summary The new complexes K₂[Ni(H₂heo)₂]·3H₂O, K₂[Pd-(H₂heo)₂], K₂[Cu(heo)]·3H₂O and [Cu₂(heo)·2H₂O] {heo = [(CONCH₂CH₂O)₂]^4-} were prepared and characterized by chemical analyses, conductivity measurements, thermogravimetry, magnetic susceptibility and i.r. and u.v. spectroscopy.Monomeric square planar structures with MN₄ coordination spheres are found for the nickel and palladium complex anions.For copper, two different complexes were identified. In slightly alkaline media, a green insoluble nonelectrolyte [Cu₂(heo)·2H₂O] was prepared; the two copper(II) centres are bridged by the tetra-deprotonated ligand in a trans-planar configuration with the H₂O molecules strongly coordinated to the copper(II). The copper(II) monomer has been prepared in strong alkaline media, this anion also contains the tetra-deprotonated ligand in a planar trans form.