叔胺N235-PtCl6^2- -HCI萃取体系第三相中“超浓盐酸”的生成及其微乳结构

采用分子谱学及同步辐射X射线小角散射（SAXS）等表征手段,研究了三烷基叔胺（N235）莘取PtCl6^2-体系中第三相的形成及溶液微观聚集态结构的变化对PtCl6^2-萃取行为的影响．实验结果表明：萃铂有机相中第三相的形成与萃入有机相的酸和水含量的变化导致溶液结构发生变化有关：与含铂高酸度盐酸水溶液平衡后,第三相微乳水团中形成H^＋／H2O摩尔比远大于37wt％常规饱和浓盐酸的“超浓盐酸”;“超浓盐酸”微观介质内H^＋和Cl^-的大量聚集增浓对Pt离子的络合配位状态产生影响,H^＋参与了Pt离子配位状态的转变：第三相“超浓盐酸”形成后,使得微乳水团中大量存在的H^＋有可能参与调控水团中各种HmPtCl6^z＋复合络离子配位状态的相对含量,被H^＋活化的叔胺（R3NH^＋）与Pt离子的各种配位状态的匹配程度最终决定了铂在第三相中的萃取行为．     

2-乙基己基辛基硫醚树脂固相萃取钯的研究

合成和鉴定了新萃取剂2-乙基己基辛基硫醚(EHOS),研究了EHOS树脂萃取钯的性能。实验表明,在0.1 mol·L^-1盐酸介质中,EHOS树脂萃Pd(Ⅱ)的萃取率＞99%,研究了EHOS树脂萃取钯的机理,结果表明,EHOS树脂通过EHOS分子上的硫原子与钯(Ⅱ)配位,形成2∶1配合物。硫脲是有效反萃剂,从萃合物的晶体结构看出,硫脲通过S原子与Pd(Ⅱ)配位,萃合物以Pd原子为中心构成平面正方型结构。选择了汽车催化剂浸出液进行固相萃取分离试验,钯回收率＞97%。     

N_(235)萃取HCl体系中TBP消除第三相的作用机理

通过测定萃取有机相的电导率变化研究叔胺N235(三烷基胺)萃取盐酸体系中第三相的形成及改性剂消除第三相的作用机理。实验结果表明,无改性剂时萃取体系在各种条件下均出现第三相。第三相组成为R3NH (H2O)3·Cl-,具有导电性。加改性剂TBP(磷酸三丁酯)后,第三相消失。本文认为改性剂TBP消除第三相的作用机理是TBP能够将萃合物R3NH (H2O)3·Cl-拆分为可溶于惰性稀释剂的R3NH (H2O)3·O=P(OC4H9)3大阳离子,Cl-离子则以抗衡离子分散于稀释剂中。     

磷酸三丁酯/正辛醇络合萃取对氯苯酚

以对氯苯酚稀溶液为研究对象,以正辛醇为稀释剂,研究了萃取剂种类及其浓度、水相平衡pH、对氯苯酚初始浓度等因素对萃取分配比的影响,并用NaOH对其负载溶质的有机相进行反萃.结果表明,络合萃取对处理高浓度对氯苯酚废水具有优势;磷酸三丁酯(TBP)的浓度和体系的pH是影响络合萃取的关键因素;采用NaOH对有机相进行反萃,当NaOH浓度为0.5mol/L时反萃率达到98.55%.红外光谱分析表明,TBP萃取对氯苯酚基于氢键作用机理.     

十四烷基二甲基苄基氯化铵萃取Au(CN)2-的微观机理

通过萃取平衡、傅里叶变换红外光谱及分峰技术研究了季铵盐十四烷基二甲基苄基氯化铵(TDM-BAC)-磷酸三丁酯(TBP)-正庚烷体系萃取Au(CN)₂^-的机理及过程.提出了萃合物的结构模型是基于氢键的超分子体系,组成为[R₄N⁺]·[Au(CN)₂^-]·4H₂O·4TBP.当有机相金浓度大于3g·L^-1时,有机相中存在聚集现象.通过激光光散射技术测定了有机相中反向胶团的大小,表明萃取过程是分散在水相中的胶团在协萃剂(或助表面活性剂)作用下溶入有机相,转型为反向胶团或微乳液(W/O型)聚集状态.     

TBP对含钛原料酸浸液中盐酸的萃取分离

研究了TBP(磷酸三丁酯)对盐酸的萃取和反萃性能。萃取过程研究和红外光谱分析结果表明:盐酸以TBP·HCl的形式进入有机相,萃取速度很快,一分钟达萃取平衡。盐酸萃取率随萃取剂浓度的增加而增加,而对钙、镁、铝无萃取性能,可实现含钛原料酸浸液中盐酸的萃取分离。以水为反萃剂,可有效反萃萃取液中的盐酸。模拟逆流萃取,绘制了以100%TBP为萃取剂,对6 mol·L~(-1)盐酸进行萃取的萃取-反萃等温线。     

Pd/PdO纳米复合微球的合成及催化性能

采用甲基丙烯酸锌加速还原氯化钯(PdCl₂) 溶液中的钯离子(Pd ²⁺)为钯(Pd) 纳米微球, 进而用得到的钯纳米微球直接制备钯/氧化钯(Pd/PdO) 纳米复合微球. 通过扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 粉末X射线衍射分析(XRD)及X射线光电子能谱分析(XPS) 等方法对 Pd/PdO 纳米复合微球进行表征, 结果表明, 制备的纳米复合微球为表面粗糙、 大小均一的纳米微球. 采用紫外-可见吸收光谱(UV-Vis) 等方法考察了 Pd/PdO 纳米复合微球在对硝基苯酚(4-NTP) 还原反应中的催化性能, 发现其具有良好的催化活性和循环稳定性.     

二已基-N,N-二乙基酰胺甲撑磷酸酯从盐酸介质中萃取钯(Ⅱ)的研究

研究了DHDECMP的二甲苯溶液从盐酸溶液中对钯(Ⅱ)的萃取。钯(Ⅱ)的分配比随水相盐酸浓度和有机相萃取剂浓度的增加而增加。当水相盐酸浓度大于0.5mol·l~(-1)时,萃取平衡可表示为 pd~(2 ) 2H~ 4Cl~- 2DHDECMP-(o)(?)[PdCl_4~(2-)·2H~ DHDECMP]_(o) DHDECMP以及萃取平衡后有机相的红外吸收谱表明,DHDECMP中的P=O基被质子化后与PdCl_4~(2-)缔合成离子对进入有机相而使Pd(Ⅱ)被萃取。     

萃取法去除硫酸氧钛液中杂质铁

采用溶剂萃取法有效去除了钛白粉制备过程中的中间产物硫酸氧钛液中大量的杂质铁。 将硫酸氧钛液中的Fe2+氧化成Fe3+后,用磷酸三丁酯(TBP)和煤油混合体系萃取除去Fe3+。 考察了氧化剂、稀释剂、有机相中TBP体积分数、萃取相比、NaCl加入量等对铁萃取率的影响以及反萃条件的选择和萃取剂的循环使用效果,结果表明,用煤油作稀释剂,TBP在有机相的体积分数为60%,萃取相比O/W为2∶1时,NaCl加入量以Cl-计4 mol/L,Fe3+的3次萃取率可达99%,钛的损失率低至0.4%。当反萃相比W/O为1∶1时,Fe3+的3次反萃率可达100%。TBP经过5次萃取-反萃循环使用后,对Fe3+的萃取率无明显下降,可循环使用。     

甲基膦酸二(1-甲基庚基)酯萃取金(Ⅲ)的紫外光谱研究

中性含磷萃取剂萃取贵金属已有报道.Tocher等研究了磷酸三丁酯(TBP)和三辛基氧膦(TOPO)对HAuCl_4和HAuBr_4的萃取,用分配比法测定了萃合物的组成为H_3O~+·3R·yH_2O…AuX_4~-.陈景等研究了TBP和烷基氧膦(TAPO)对铂族金属萃取,发现TBP萃取HIrCl_6时,IrCl_6~(2-)萃取前后的中心离子光谱没有发生变化;萃取H_2PtCl_6时,纯TBP及萃合物红外光谱中P=O的振动频率几乎无改变.由此推断,萃取剂未与被萃离子发生配位作用,而是形成了离子缔合物2(H~+·nTBP·yH_2O)…MCl_6~(2-).可见,这类萃取剂在萃取贵金属时,首     

Formation of super-concentrated hydrochloric acid in the third phase in tertiary amine N235-PtCl 6 2− -HCl system and its influences on the Pt microemulsion extraction

In this paper, we have investigated the formation of the third-phase in tertiary amine (N235)-PtCl ₆ ^2? -HCl system and the microscopic phase structural evolution of platinum-loaded organic phases before and after the occurrence of the third-phase. The third-phase is characterized by various spectroscopic techniques, and the small angle X-ray scattering (SAXS) experiments demonstrate the appearance of nano-aggregates, i.e., water-in-oil reversed micelles, in the third phase. The experimental results indicate that (1) formation of the third phase is related to the aggregation behaviors of nano-reversed micelles in which a super-concentrated hydrochloric acid formed with the H⁺ to H₂O molar ratio being much higher than that of the conventional 37 wt% saturated hydrochloric acid. (2) The occurrence of the super-concentrated HCl results in a great amount of H⁺ and Cl^? ions enriched and confined within the nano-water pools of W/O reversed micelles in third phase. Therefore, the coordination behaviors of platinum complex ions in that super-concentrated hydrochloric acid are very different from their corresponding behaviors in bulk aqueous solutions. It is possible that H⁺ ions participate in the formation of such complexes as H _m PtCl ₆ ^z+ in the super-concentrated hydrochloric acid. (3) The relative contents of various H _m PtCl ₆ ^z+ complexes are different corresponding to the H⁺ ion concentrations in confined nano-water pools. The association ability of the acidified tertiary amine N235 molecules (R₃NH⁺) with various H _m PtCl ₆ ^z+ complexes plays an important role in affecting the platinum extraction behaviors.     

Highly specific spectrophotometric method for palladium(II) determination with 3-(5'-tetrazolylazo)-2,6-Diaminotoluene in the presence of chlorides. Kinetic and equilibrium study of reactions

3-(5'-tetrazolylazo)-2,6-Diaminotoluene (TEADAT, H(3)L(2+)) forms stable 1:1 and 1:2 (metal:ligand) pink-red complexes (lambda(max) 506 and 536 nm) with palladium(II). The apparent molar absorptivity of 1:2 complex is 5.2 x 10(4) 1.mol(-1). cm(-1) at 536 nm. Equilibrium constants beta*(nl) for reactions PdCl(2-)(4) + nH(3)L(2+) right harpoon over left harpoonright harpoon over left harpoon PdCl(4-n) (H(2)L)(2n-2)(n) + n Cl(-) + n H(+) were determined: logbeta*(1) = 4.09 +/- 0.05, logbeta*(2) = 8.40 +/- 0.02, corresponding stability conditional constants of PdCl(3)(H(2)L) and PdCl(2)(H(2)L)(2+)(2) were log beta(1) = 19.03, log beta(2) = 26.74. The formation of complexes was rather slow but could be speeded up considerably by the catalytic effect of trace amounts of thiocyanate. Constant absorbance values were thus reached in 2-5 min. A rapid, sensitive and highly specific method for the determination of palladium(II) at pH 1.42 in 0.25M NACl has been worked out with a detection limit of 0.54 mug. Interference of precious and common metal ions have been studied and the method has been applied for the determination of palladium in Pd asbestos, oakay alloys and various catalysts and for the determination of palladium in precious metals.     

Simple route to the doubly ortho-palladated azobenzenes: building blocks for organometallic polymers and metallomesogens

A new class of doubly cyclopalladated complexes, {PdCl(dmf)}2(mu-azb) (1) and {PdCl(dmf)}2(mu-aazb) (2), has been prepared in dimethylformamide (dmf) by reaction of azobenzene (azb) and 4-aminoazobenzene (aazb), respectively, with an excess of PdCl2(CH3CN)2 complex. Recrystallization of 1 and 2 in dimethyl sulfoxide (dmso) yields complexes {PdCl(dmso)}2(mu-azb) (3) and {PdCl(dmso)}2(mu-aazb) (4), respectively. The crystal structures of 1 and 4 have been determined by X-ray diffraction. All complexes are characterized by 1H and 13C NMR spectra and elemental analysis. In both crystal structures, solvent molecules are bound to palladium through oxygen atoms and oriented trans to carbon. In view of greater preference of palladium to nitrogen and sulfur atoms, the experimental structures were rationalized by quantum-chemical calculations and confirmed as the most stable isomers.     

Influence of O/S/Se Exchange on the Stability of 1,3,4-Selana(Thia/Oxa)Diazole-Palladium Complexes as Studied by Electrospray Ionization Mass Spectrometry

Abstract

The complexes of 2-phenyl-1,3,4-selena(thia/oxa)diazole with a palladium cation were studied by using electrospray ionization mass spectrometry. Palladium chloride was used as a source of palladium cations. The complexes of ligand:metal stoichiometry of 3:1 (ions [L₃+PdCl]⁺) were formed for selenadiazoles and thiadiazoles. Quantum mechanical calculations performed indicated that ligand molecules are attached to palladium cation by the N-4 atom. The fragment ions formed [L₂–H+Pd]⁺ may be regarded as organometallic species. Selenadiazoles were found more prone to form the palladium complexes than thiadiazoles. Oxadiazoles did not yield the respective palladium complexes. For comparison, the nickel cation was also included in the study but only 1:1, and less abundant 2:1 complexes were observed. Exchange of selenium into oxygen does not affect the abilities of the ligands to form nickel complexes.     

Synthesis of beta-P,N aminophosphines and coordination chemistry to Pd(II). X-ray structures of [PdCl2(Ph2PCH(Ph)NHPh-kappaP,kappaN)] and PdCl(eta3-C3H5)(Ph2PCH2CH(Ph)NHPh-kappaP)

The reaction of the C=N bond in PhCH=NPh with the carbanionic species Ph2PCH2-, leading to the N-phenyl beta-aminophosphine Ph2PCH2CH(Ph)NHPh, L1, is described. This molecule reacts with different organic electrophiles to afford related compounds Ph2PCH2CH(Ph)NPhX (X = SiMe3, L2; COPh, L4), [Ph2MePCH2CH(Ph)NHPh]+(I-), L3, and [Ph2PCH2CH(Ph)N(Ph)CO]2, L5, containing two amido and two phosphino functions. The coordination properties of L1, L2, and L4 have been studied in palladium chemistry. The X-ray structure of [PdCl2(Ph2PCH2CH(Ph)NHPh-kappaP,kappaN)] shows the bidentate coordination mode for the L1 ligand with equatorial C(Ph)-N(Ph) phenyl groups. [PdCl2(Ph2PCH2CH(Ph)NHPh-kappaP,kappaN)] crystallizes at 298 K in the space group P2(1)/n with cell parameters a = 10.689(2) A, b = 21.345(3) A, c = 12.282(2) A, beta = 90.294(12) degrees, Z = 4, D(calcd) = 1.526. The reaction between 2 equiv of L1 and [PdCl(eta3-C3H5)]2 affords the [PdCl(eta3-C3H5)(Ph2PCH2CH(Ph)NHPh-kappaP)] complex in which an unexpected N-H.Cl intramolecular interaction has been observed by an X-ray diffraction analysis. [PdCl(eta3-C3H5)(Ph2PCH2CH(Ph)NHPh-kappaP)] crystallizes at 298 K in the monoclinic space group Cc with cell parameters a = 10.912(1) A, b = 17.194(2) A, c = 14.169(2) A, beta = 100.651(9) degrees, Z = 4, D(calcd) = 1.435. Neutral and cationic alkyl or allyl palladium chloride complexes containing L1 are also reported as well as a neutral allyl palladium chloride complex containing L4. Variable-temperature 31P[1H] NMR studies on the allyl complexes show that the eta3/eta1 allyl interconversion is enhanced by a positive charge and also by a N-H.Cl intramolecular interaction.     

Self-assembly of polymer and sheet structures in palladium(II) complexes containing carboxylic acid substituents

A series of complexes trans-[PdCl(2)L(2)] has been prepared by the reaction of [PdCl(2)(PhCN)(2)] and/or Na(2)[PdCl(4)] with L = pyridine or quinoline ligands having one or two carboxylic acid groups. These complexes can form 1-D polymers through O-H.O hydrogen bonding between the carboxylic acid groups, as demonstrated by structure determinations of [PdCl(2)(NC(5)H(4)-4-COOH)(2)], [PdCl(2)(NC(5)H(4)-3-COOH)(2)], and [PdCl(2)(2-Ph-NC(9)H(5)-4-COOH)(2)]. In some cases, solvation breaks down the O-H.O hydrogen-bonded structures, as in the structures of [PdCl(2)(NC(5)H(4)-3-COOH)(2)].2DMSO and [PdCl(2)(2-Ph-NC(9)H(5)-4-COOH)(2)].4DMF, while pyridine-2-carboxylic acid underwent deprotonation to give the chelate complex [Pd(NC(5)H(4)-2-C(O)O)(2)]. The complexes trans-[PdCl(2)L(2)], L = pyridine-3,5-dicarboxylic acid or 2,6-dimethyl pyridine-3,5-dicarboxylic acid, self-assembled to give 2-D sheet structures, with hydrogen bonding between the carboxylic acid groups mediated by solvate methanol or water molecules. In the cationic complexes [PdL'(2)L(2)](2+) (L'(2) = Ph(2)PCH(2)PPh(2), Ph(2)P(CH(2))(3)PPh(2); L = pyridine carboxylic acid; anions X(-) = CF(3)SO(3)(-)), hydrogen bonding between the carboxylic acid groups and anions or solvate acetone molecules occurred, and only in one case was a polymeric complex formed by self-assembly.     

Ion flotation of rhodium(III) and palladium(II) with anionic surfactants

The ion flotation of rhodium(III) and palladium(II) with some anionic surfactants has been investigated. Two flotation procedures are proposed for the separation of some platinum metals, based on differences in the kinetic properties of the chloro-complexes of rhodium(III), palladium(II) and platinum(IV). The first involves the selective flotation of Rh(H(2)O)(3+)(6) from PdCl(2-)(4) and PtCl(2-)(6) in dilute hydrochloric acid with sodium dodecylbenzenesulfonate (SDBS). After precipitation of the hydroxide and redissolution in dilute acid, the Rh(III) is converted into Rh(H(2)O)(3+)(6), Pd(II) and Pt(IV) remaining as PdCl(2-)(4) and PtCl(2-)(6) respectively, and separation is achieved by floating the Rh(H(2)O)(3+)(6) with SDBS. The second is for separation of Pd(II). Prior to flotation, the solution of PdCl(2-)(4) and PtCl(2-)(6) is heated with ammonium acetate to convert PdCl(2-)(4) into Pd(NH(3))(2+)(4). The chloro-complex of Pt(IV) is unaffected. The complex cation, Pd(NH(3))(2+)(4), is then selectively floated with SDBS. The procedures are fast, simple and do not require expensive reagents and apparatus.     

Highly active,air-stable palladium catalysts for the C-C and C-S bond-forming reactions of vinyl and aryl chlorides: use of commercially available [(t-Bu)(2)P(OH)](2)PdCl(2), [(t-Bu)(2)P(OH)PdCl(2)](2), and [[(t-Bu)(2)PO...H...OP(t-Bu)(2)]PdCl](2) as catalysts

Air-stable palladium complexes [(t-Bu)(2)P(OH)](2)PdCl(2), [(t-Bu)(2)P(OH)PdCl(2)](2), and [[(t-Bu)(2)PO...H...OP((t-Bu)(2)]PdCl](2) serve as efficient catalysts for a variety of cross-coupling reactions of vinyl and aryl chlorides with arylboronic acids, arylzinc reagents, and thiols to yield the corresponding styrene derivatives, biaryls, and thioethers. (31)P NMR and mechanistic studies argue that the phosphinous acid ligands in the complexes can be deprotonated in the presence of a base to yield an electron-rich anionic species, which is likely a catalyst intermediate, and dimeric [[(t-Bu)(2)PO...H...OP((t-Bu)(2)]PdCl](2) was isolated and cystallographically characterized. These anionic complexes are anticipated not only to accelerate the rate-determining oxidative addition of aryl chlorides but also to stabilize the palladium complexes in the catalytic cycle.     

Separation of trace amounts of palladium (II) with crown ether from hydrochloric acid and potassium thiocyanate media

A new method for the separation of trace amounts of palladium from hydrochloric acid and potassium thiocyanate media has been established based on the formation of an ion-pair complex of palladium thiocyanate anion Pd(SCN)4(2-) and the cationic potassium complex of dicyclohexyl- 18-crown-6 (DC18C6) in chloroform. The effect of various factors (solvent, crown ether, potassium thiocyanate, hydrochloric acid, reagent concentration, shaking time, phase volume ratio, composition of the extracted species, foreign ions, etc.) on the extraction and back-extraction of palladium has been investigated. The method can be combined with subsequent FAAS determination of palladium. The procedure was applied to determine palladium traces in chloroplatinic acid and rhodium chloride.