乙酰丙酮铂(Ⅱ)、钯(Ⅱ)配合物的XPS和NMR特性研究

本文研究了乙酰丙酮铂（Ⅱ）、乙酰丙酮钯（Ⅱ）的光电子能谱和核磁共振谱的特性,提出了乙酰丙酮与Pt（Ⅱ）、Pd（Ⅱ）的配位方式,认为除了形成M←L的σ配位键外,还形成了M→L的dxz（dyz）→π^13反馈π键,从而解释了乙酰丙酮与Pt（Ⅱ）、Pd（Ⅱ）形成稳定配合物的原因.     

乙酰丙酮在Ir( acac)3和Ir(acac)3(H2O)中的配位方式研究

采用核磁共振谱( 13C、1H- NMR)和单晶X射线衍射对乙酰丙酮在铱配合物Ir( acac)3和Ir( acac)3(H2O)中的配位方式进行了深入研究,证实了乙酰丙酮与铱之间的配位方式有2种,即氧键配位和碳键配位.     

乙酰丙酮铑(Ⅲ)的化学性质

合成了乙酰丙酮铑, 并采用紫外、红外、核磁和质谱等手段研究了乙酰丙酮铑(Ⅲ)的化学结构特征. 结果表明: 乙酰丙酮铑属于低自旋的惰性配合物; 由于配合物中离域π键的形成, 配体羰基已不具备典型的羰基特征; 在快原子的轰击下, 乙酰丙酮铑的配位键逐一断裂, 释放出游离的乙酰丙酮, 最后形成103Rh , 同时伴随共价键的断裂与重排; 在磁场中, 由于Rh3 的强吸电子效应以及螯合环的环电子流效应, H核化学位移向低场移动. 通过TG-DTA和GC-MS分析并探讨了乙酰丙酮铑的热分解行为, 为其应用提供了热学依据和理论参考, 并建议以300.℃作为以乙酰丙酮铑为前驱体的CVD铑沉积工艺的沉积温度.     

乙酰丙酮铂族金属有机配合物的合成现状及用途

结合昆明贵金属研究所化学与药物研究室中进行的乙酰丙酮铂族金属有机配合物的合成工作,简要介绍了乙酰丙酮铂族金属有机配合物合成现状,并概述了乙酰丙酮铂族金属有机配合物的用途.     

冠状四核钯(Ⅱ)配合物的合成和晶体结构

合成了一种用作前驱体的、中性、具有冠状结构的新型水溶性四核钯配合物十一水·醋酸亚胺合钯([CH_3COO)_4Pd_4(NH_2)_4]·11H_2O),用元素分析和X射线单晶衍射仪(XRD)对其结构进行了表征,用热重-差热(TG-TDA)测试其热分解特性。结果表明,该化合物为正交晶系、Pccn空间群,其晶体它的结构是以4个(CH_3COO)Pd片段分别和4个-NH_2配体桥接,形成八原子的环状四核钯的配合物,也获得了该配合物的键长和键角等参数。TG-DTA测试显示化合物分解峰出现在231.4℃(低分解温度),该配合物中不含氯、膦和硝酸根,可作为新型的钯前驱体。     

用乙酰丙酮钯作前驱物制备Pd/C催化剂的研究

分别采用乙酰丙酮钯、氯化钯和硝酸钯作前驱物,用浸渍-还原法制备了一系列Pd/C催化剂,以松香歧化反应评价其活性,研究了活性炭类型、载体预处理、溶剂、还原方法及温度等因素对Pd/C催化剂活性的影响.结果表明,采用具有较大比表面积和孔容的活性炭作载体有利于钯在其表面的均匀分布和催化剂活性的提高;以Pd(acac)2作前驱体,以及使用极性较强的溶剂与用无机配合物前驱体相比,制备的Pd/C催化剂活性较高;TG-DTA分析表明Pd(acac)2在350℃下完全分解,基于此结果,作者在350℃条件下采用氢气干法还原,制备出活性略高于从日本进口的Pd/C催化剂.     

乙酰丙酮钯(II)的热分解行为

采用热重-差热(TG-DTA)与气-质联用(GC-MS)研究了CVD技术制备钯膜材料的前驱体乙酰丙酮钯[Pd(acac)2]的热分解行为。通过对比其在空气和氩气两种气氛、不同温度下的热裂解产物,认为在以乙酰丙酮钯为前驱体通过CVD技术制备钯膜时,空气比氩气更适合做载气。     

乙酰丙酮钯（Ⅱ）的热分解行为

采用热重-差热（TG-DTA）与气-质联用（GC-Ms）研究了CVD技术制备钯膜材料的前驱体乙酰丙酮钯[Pd（acac）2]的热分解行为。通过对比其在空气和氩气两种气氛、不同温度下的热裂解产物，认为在以乙酰丙酮钯为前驱体通过CVD技术制备钯膜时，空气比氩气更适合做载气。     

蓝光铱配合物的合成、结构表征及光物理性能测试

在碱性条件下,以铱的氯桥二聚体(dfppy)2Ir(μ-Cl2)Ir(dfppy)2和乙酰丙酮反应合成出高效磷光材料二[2-(2,4-二氟苯基)吡啶-C2,N'](乙酰丙酮)合铱(III)(Ir(dfppy)2(acac))。用核磁共振谱(1H NMR、13C NMR)、红外光谱和单晶X射线衍射等表征手段确定了分子结构,用高效液相色谱法测定了纯度,用光致发光光谱测试了光物理性能。结果表明,合成的配合物组成及结构与实际一致,Ir(dfppy)2(acac)为电中性八面体配合物,Ir-O、Ir-C、Ir-N键的平均长度分别为0.2160(14)、0.1998(11)、0.2030(15)nm,在484 nm处出现了较强的蓝光发射。方法的合成产率大于90%,纯度99.70%,适于批量制备。     

TADAB分光光度法测定微量钯

对新试剂TADAB与钯的显色反应研究结果表明,在1.2 mol/dm~2高氯酸介质中,钯与TADAB形成1∶1的稳定配合物.其最大吸收位于584nm,TADAB的最大吸收位于411nm.配合物的表观摩尔吸光系数ε_(584)=5.84×10~4dm~3·mol~(-1)·cm~(-1),桑德尔灵敏度S=0.00182μg·cm~(-2).钯的浓度在5～50μg/25ml符合比尔定律.     

Lanthanide complexes with acetylacetonate and 5,10,15,20-tetra[para-(4-flourobenzoyloxy)-meta-ethyloxy]phenylporphyrin

Lanthanide complexes of acetylacetonate and 5,10,15,20-tetra[para-(4-flourobenzoyloxy)-meta-ethyloxy]phenylporphyrin having the general formula Ln[(FBOEP)₄P]acac (where Ln=Ho, Er, Yb, Lu; FBOEP=[para-(4-flourobenzoyloxy)-meta-ethyloxy]phenyl; Hacac=acetylacetone; P=porphyrin) have been prepared and characterized. A structure is proposed in which one 5,10,15,20-tetra[para-(4-flourobenzoyloxy)-meta-ethyloxy]phenylporphyrin is coordinated to a rare earth ion in a tetradentate fashion, while one acetylacetonate is coordinated to the same metal ion in a bidentate fashion. We investigated the photo-generated charge behavior of the ligand and the complex, Lu[(FBOEP)₄P]acac, by means of surface photo-voltage spectroscopy (SPS) and field induced surface photo-voltage spectroscopy (FISPS) which are useful tools to investigate the photo-physics of excited states generated by absorption in the aggregate state.     

Electrochemical behaviour of some transition metal acetylacetonate complexes as corrosion inhibitors for mild steel

Corrosion inhibition of some metal acetylacetonate complexes including Co(acac)₂, Cu(acac)₂, Mn(acac)₂ and Zn(acac)₂ was evaluated using electrochemical impedance spectroscopy (EIS) in 3.5% NaCl for mild steel. The results were compared to zinc potassium chromate (ZPC) solution in 3.5% NaCl. Corrosion inhibition of these metal complexes followed the order: ZPC > Co(acac)₂ > Zn(acac)₂ > Mn(acac)₂ while Cu(acac)₂ displayed corrosion catalytic activity. Solutions containing metal acetylacetonate complexes had an increase in pH compared to Blank and ZPC solutions, which indicated partial dissociation of ligand and metallic cations. However, after 24-h contact with the mild steel samples the solutions pH were dropped which implied decrease of the complex concentration in the test solutions. SEM images showed no detectable deposited film on the surface exposed Co(acac)₂ solution while EDX analysis revealed precipitation of a layer containing 4.14% Co. SEM-EDX results for samples immersed in Zn(acac)₂ and Mn(acac)₂ solution showed precipitation of Zn and Na components and Mn complex on the surface, respectively.     

Development of efficient solution-processed red phosphorescent organic light-emitting diodes using carrier transport materials

We report on efficient solution-processed red emissive phosphorescent organic light-emitting diodes (PhOLEDs) employing bis[9-ethyl-3-(4-phenylquinolin-2-yl)-9H-carbazolato-N,C²′]iridium acetylacetonate (Et-Cvz-PhQ)₂Ir(acac) and bis[9-(2-(2-methoxyethoxy)ethyl)-3-(4-phenylquinolin-2-yl)-9H-carbazolato-N,C²′]iridium acetylacetonate (EO-Cvz-PhQ)₂Ir(acac) doped into polymer host PVK, blended with electron transporting material OXD-7, and optimized concentration of carrier-transporting material TPD. The optimized PhOLEDs doped with 16 wt% carrier-transporting material shows a maximum luminance efficiency and power efficiency of 4.66 cd/A and 1.22 lm/W, which were increased by 40% and 20%, respectively, compared with that of reference device. The electroluminescence (EL) spectra exhibited the characteristic spectrum of (Et-Cvz-PhQ)₂Ir(acac) and (EO-Cvz-PhQ)₂Ir(acac) with its maximum at 630 nm and CIE (Commission International de L’Eclairage) coordinate of (0.66, 0.33).     

A study on the composition and structure of cyclic sulfoxide derivative palladium(Ⅱ) complex

The composition and structure of cyclic sulfoxide derivative Pd(Ⅱ) complex were investigated. The coordinated number was studied with slope method. The coordination number is 2 in lower acidity, but it is 3 in higher acidity. Four methods, UV (ultraviolet) spectra, FrIR (Fourier transform infrared) spectra, 1H-NMR (nuclear magnetic resonance)spectra, and 13C-NMR spectra, were used to determine the coordinated atom in complex. Pd is coordinated with O and S atom in S=O group in lower acidity media. The conversion of coordination bond appears with an increasing time. Pd is coordinated with S atom in S=O group in higher acidity media, and inter-ligand-transfer reaction occurs.     

2-丁基-四氢噻吩亚砜及其钯配合物异构体的理论研究

采用多种理论研究方法对2-丁基-四氢噻吩亚砜(BTHTO)及其钯配合物进行几何优化,发现BHandH/6-31G*法所得构型最优,从理论上研究BTHTO与钯(II)的配合模式及其分子稳定性的关系.结果表明Pd-O配位的A模式能量最高,Pd-S配位的B模式能量最低最稳定,而混合配位的C模式能量稍高于B.环状亚砜中的氧原子处于分子的外侧,所受位阻较小,配位速度较快;硫原子受环状结构和侧链影响,位阻较大,配位速度较慢.在萃取过程中,萃合物以硫氧混合配位的C模式形成,随时间的增加,氧配位转化为硫配位即B模式,能量达到最低值,为热力学的稳定状态.     

双[2-(对甲苯基)吡啶]乙酰丙酮合铱的合成及结构表征

以水合三氯化铱为原料,2-(对甲苯基)吡啶作环金属配体、乙酰丙酮作辅助配体合成了双[2-(对甲苯基)吡啶]乙酰丙酮合铱[(tpy)2Ir(acac)],通过质谱、氢谱、X射线单晶衍射分析表征手段确证了其分子结构。通过紫外可见光谱和光致发光光谱分析,研究了该配合物的光物理性能,在410和461 nm处有单重态和三重态吸收,在516 nm处有较强的绿光发射,表明该配合物是一种绿光材料。     

有机膦配体对钯分子偶联催化剂活性的影响

采用3种不同的有机膦配体,设计和合成出3个有机膦钯(II)配合物,测试和表征了它们的化学结构,分别为trans-{Pd[(t-Bu)2PPh]2Cl2}、trans-[Pd(Amphos)2Cl2]、cis-[Pd(Xantphos)Cl2] ((t-Bu)2PPh=二叔丁基苯基膦、Amphos=二叔丁基-(4-二甲基氨基苯基)膦、Xantphos=4,5-双二苯基膦-9,9-二甲基氧杂蒽)。在2个Suzuki和1个Sonogashira偶联反应模型上,测定了它们的催化活性,考察了膦配体对钯分子偶联催化剂活性的影响,发现膦配体对催化活性有重要影响,且对应不同的反应模型其影响程度不同,影响机制与膦配体的配位能力和分子的空间体积有关。     

Synthesis and characterization of polyaluminocarbosilane as SiC ceramic precursor

Polyaluminocarbosilane (PACS) was synthesized by the reaction of aluminum acetylacetonate (Al(AcAc)3) with polysilacarbosilane (PSCS), which was prepared by thermolysis and condensation of polydimethylsilane (PDMS). The sublimation of Al(AcAc)3 could be avoided by the use of PSCS as reactant. The empirical formula of PACS was SiC2.01 H7.66O0.13 Al0.02, which has the relative molecular mass of 2 265. When the reaction of PSCS with Al(AcAc)3 proceeds, an enormous decrease in the number of Si-H bonds in PSCS is observed, at the same time, gas acetylacetonate is a by-product of the reaction based on the ligands of Al(AcAc)3. The reaction mechanism is found to be related to the increase in the molecular mass of PACS by the cross-linking reaction of Si-H bonds in PSCS with Al(AcAc)3, which leads to the formation of Si-Al bonds.     

铜存在下络合滴定钯

考察了硫脲与Ｃｕ（Ⅱ）、Ｐｄ（Ⅱ）的ＥＤＴＡ络合物的反应。研究表明，一定条件下硫脲能迅速地与Ｐｄ（Ⅱ）结合释放出等量的ＥＤＴＡ，再与Ｃｕ（Ⅱ）反应，因而可在Ｃｕ（Ⅱ）存在下络合滴定钯。     

碳载PtNi合金催化剂的制备、表征及氧还原催化性能研究

以乙酰丙酮铂(Pt(acac)₂)、乙酰丙酮镍(Ni(acac)₂)为前驱体,三正辛基氧膦(TOPO)为表面修饰剂,油胺(OAm)为还原剂,N,N-二甲基甲酰胺(DMF)为助剂,超导碳科琴黑ECP为载体,采用液相合成法制备了碳载PtNi合金纳米催化剂(Pt_2.7Ni/C)。通过TEM对其形貌进行表征,ICP-AES进行定性和定量分析,XRD对其结构进行表征,并进行电化学阴极氧还原催化性能研究。研究表明：所制备的Pt_2.7Ni/C纳米催化剂粒径分布在3～11 nm之间,平均粒径为6.25 nm;在酸性条件下,当电位在0.9 V(vs.RHE)时,Pt_2.7Ni/C纳米催化剂的质量比活性为796.08 mA·mg_Pt^-1,为商业Pt/C(JM)催化剂的约4.0倍,面积比活性为3.60 mA·cm^-2,为商业Pt/C(JM)催化剂的约11.3倍。同时在经过5000和10 000次的加速耐久性实验后,Pt_2.7...