电感耦合等离子体原子发射光谱（ICP-AES）法测定高镍铜液体样品中金、钯、铂

为实现中控液体物料中金、钯、铂元素的精准定量分析,为工艺生产定向富集和高效提取提供数据支持,本文建立了ICP—AES法测定中控冶炼系统中高镍铜液体样品中金、铂和钯3种元素含量的测定方法。确定了试液用碲共沉淀,贵金属进入滤渣,经火试金分离富集得到贵金属合粒,合粒经王水溶解后,于王水介质中在电感耦合等离子光谱仪上同时测定金钯铂的量。该方法金、铂、钯的测定范围为 0.014mg/L～5mg/L,回收率为92.2%～104.4%, RSD为3.21%～10.58%,方法满足高镍、铜液体样品中金、钯、铂元素的测定。     

Preparation and characterization of tris(iso‐propyl)stibine complexes of palladium and platinum

Tris(iso‐propyl)stibine complexes of palladium and platinum of the type [MX₂(SbⁱPr₃)₂] [M, X = Pd, Cl (1a), Pd, Br (1b), Pd, I (1c), Pt, Cl (2)] have been prepared and characterized by elemental analysis, IR and ¹H NMR spectral data. The structure of 1a, established by X‐ray structural analysis, revealed that the palladium atom is in a square planar environment with mutually trans SbⁱPr₃ ligands. Copyright © 2001 John Wiley & Sons, Ltd.     

Determination of platinum, palladium and rhodium in Pt-catalysts by high performance thin layer chromatography using densitometry

The determination of palladium and platinum in alumina-supported bimetallic Pt-Re, Pd and Pt catalysts at the 0.03 and 0.3% (m/m) levels, respectively, and of rhodium and platinum in platinum sieve catalysts at the 0.04% (m/m) level and in the 4.75–19.75% (m/m) range, respectively, is described. The platinum group metals in fresh or spent catalysts are determined chromatographically using densitometry by forming theirN,N-diethyl-N-benzoylthiourea complexes. The precision of the method, %RSD, is 0.4–3.5, 2.2–6.7, and 4.2–6.0 for Pt, Pd and Rh, respectively. The accuracy was tested using alumina-based and active carbon platinum and palladium standards. The results were also compared with those obtained by FAAS. There was at most 8% difference between the results obtained with these methods, except for one active carbon based Pd standard.     

Platinum and rhodium complexes with isoleucinol-based bi- and tricyclic hydrophosphoranes

The complex formation of bi- and tricyclic hydrophosphorane derivatives of isoleucinol with [Pt(COD)Cl₂], [Rh(CO)₂Cl]₂, and [Rh(THF)₂(COD)]⁺BF₄ ^– (COD is cycloocta-1,5-diene) was investigated. In all cases, bicyclic hydrospirophosphorane selectively forms the metal chelates [M(²-PN)(X)Cl] (M = Pt, X = Cl; M = Rh, X = CO) and [Rh(²-PN)(COD)]⁺BF₄ ^–. («» denotes the residue of the hydrospirophosphorane ligand, which does not contain the P and N atoms). In addition, tricyclic hydrophosphorane (L) generates the phosphoranide complexes [Pt(¹-L)(COD)Cl]⁺Y^– (Y = Cl or BF₄). The structures of the new compounds were established by IR spectroscopy, ³¹P, ¹³C, ¹H, ²H, ¹¹B, ¹⁹F, and ¹⁹⁵Pt NMR spectroscopy, and plasma-desorption and electrospray ionization mass spectrometry. The possible mechanism of coordination of hydrophosphoranes is discussed.     

Partial molar compressibilities of halogeno complexes of platinum and palladium in aqueous solutions at 25°C

Ultrasonic propagation velocities were measured at 25°C for dilute aqueous solutions of K₂[PtX₄], K₂[PtX₆], K₂[PdX₄], and K₂[PdX₆] (X = Cl, Br, or SCN). The data obtained were combined with our previous density data to calculate the adiabatic compressibilities of each solution. Then, the infinite dilution values of partial molar adiabatic compressibilitiesK _o ^s were evaluated. By subtraction of theK _o ^s (K⁺) from those of the complexes, the values ofK _o ^s for the halogeno complex ions [PtX₄]^2-, [PtX₆]^2-, [PdX₄]^2- and [PdX₆]^2- were determined. The values for the thiocyano complex ions [Pt(SCN)₄]^2- and [Pt(SCN)₆]^2- are positive, showing that the interaction of the ligand SCN^- with the solvent water is very weak. Although the V ₂ ^o behavior of the complex ions [PtCl₆]^2- and [PdCl₆]^2- differed only slightly, compressibility measurement has indicated that the ion [PdCl₆]_2- interacts more strongly than [PtCl₆]^2-.     

Square-planar coordinated polyanions of palladium, platinum, and gold stannaborate [SnB11H11]2- coordination chemistry

The tetrasubstituted polyanions of platinum, palladium, and gold [M(SnB(11)H(11))(4)](x-) (x=6, M=Pd, Pt; x=5, M=Au) have been prepared and characterized by single-crystal X-ray diffraction, elemental analysis, IR, Raman, (11)B, and (119)Sn heteronuclear NMR spectroscopy. In the case of the platinum derivative [Bu(3)MeN](6)[Pt(SnB(11)H(11))(4)] (2) (119)Sn M?ssbauer spectroscopy has been carried out. The isolated salts are stable towards moisture and air and the complexes 2 and 3 were treated with 1,3-bis(diphenylphosphino)propane (dppp) to give the respective substitution products [Bu(3)MeN](2)[(dppp)M(SnB(11)H(11))(2)] (M=Pd, Pt).     

火试金减杂-电感耦合等离子体原子发射光谱法（ICP-AES）法测定高冰镍的金、银、铂、钯含量

建立了火试金减杂-电感耦合等离子体原子发射光谱法（ICP-AES）测定高冰镍中金、银、铂、钯含量的分析方法。实验采用火试金富集、熔融、灰吹得到合粒,通过减杂法得到银含量,通过ICP-AES法测定得到金、铂、钯含量。金、银、铂、钯的加标回收率在99.53%-101.83%之间,相对标准偏差小于3%。此方法快速、简洁,准确度高、精密度好,能够满足高冰镍的测定需求。     

Synthesis and investigation of mono- and binuclear cyano-bridged complexes of rhodium,ruthenium, and palladium

Binuclear Rh^III and Ru^II complexes of the [M¹-CN-M²]⁺BF ₄ ^– (M¹ and/or M² are (⁵-Cp)(³-C₃H₅)Rh and (⁶-C₆H₆)(³-C₃H₅)Ru) type, heteronuclear organometallic compound (⁵-Cp)(³-C₃H₅)RhCNPd(³-C₃H₅)Cl, and mononuclear Rh^III and Ru^II complexes [(³-C₃H₅)LM(MeCN)]⁺ _BF4 ^– (M = Rh, L = ⁵-Cp; M = Ru, L = ⁶-C₆H₆) were synthesized. An electrochemical study of these compounds in solutions demonstrates that the bond between the bridged CN ligand and the metal atoms is rather strong, and there is no dissociation into mononuclear fragments in solutions. The kinetics of the reaction of [(⁵-Cp)(³-C₃H₅)Rh(MeCN)]⁺ _BF4 ^– with halide ions was studied by electrochemical methods. The ligand exchange proceeds by a bimolecular dissociative-exchange mechanism.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 968–973, May, 1995.     

Transfer of heterocyclic carbene ligands from chromium to gold, palladium and platinum

The reaction of pentacarbonyl(pyrazolin-3-ylidene)chromium complexes, (2a-c) (R = Ph (a), C₆H₄NMe₂-4 (b); (C₅H₄)FeCp (c)), with [AuCl(SMe₂)], H[AuCl₄], [PdCl₂(NCPh)₂] and [PtCl₂(NCPh)₂] gives, by transfer of the heterocyclic carbene ligand, new chloro pyrazolin-3-ylidene complexes of gold(I) and gold(III), dichloro bis(pyrazolin-3-ylidene) palladium and dichloro bis(pyrazolin-3-ylidene) platinum in high yield. The chloride ligand in (Fc = (C₅H₄)FeCp) is readily displaced by trifluoroacetate. The analogous substitution of iodide for the chloride ligands in (M = Pd, Pt) give the corresponding diiodo complexes although in a much slower reaction. In contrast, the reaction of silver trifluoroacetate with affords a binuclear Pd-Ag complex containing two pyrazolin-3-ylidene and three trifluoroacetate ligands two of whom occupy bridging positions between Pd and Ag. The reactions of the pyrazolidin-3-ylidene complex (R = C₆H₄NMe₂-4) with [AuCl(SMe₂)] and [PdCl₂(NCPh)₂] yield chloro pyrazolidin-3-ylidene gold and dichloro bis(pyrazolidin-3-ylidene) palladium complexes. The related dichloro bis(tetrahydropyrimidin-4-ylidene) palladium complex is formed in the reaction of with the palladium complex [PdCl₂(NCPh)₂]. The solid-state structures of several of these heterocyclic carbene complexes including the structure of the binuclear Pd-Ag complex are established by X-ray structure analyses.     

Double carbonylation of aryl iodides with diethylamine catalyzed by dinuclear palladium complexes

Dinuclear palladium complexes bridged by a novel PNNP ligand, N,N′-bis[(2-diphenylphosphino)phenylformamidinate (dpfam), were found to be very efficient and selective catalysts for the double carbonylation of iodobenzene with diethylamine using K₃PO₄ as base and 1,4-dioxane as solvent with a TON up to 10⁵ and selectivity of 96%.     

Phosphino-aminothiazoline platinum(II) and platinum(II)/gold(I) complexes: structural, chemical and vapoluminescent properties

Phosphino-amino-thiazolines and -thiazoles can exist in solution in two tautomeric forms, in which the N-H proton involves the endo-cyclic or exo-cyclic nitrogen atom. The two tautomers show different reactivities toward alcoholysis; the imino form degrades more rapidly. Their bischelated platinum complexes were studied in the solid state by single crystal X-ray diffraction. Thus, the unique stereoelectronic features of the [Pt(PN(th))] (PN(th)=diphenylposphino-aminothiazoline) moiety were revealed. The complex cis-[Pt(PN(th))(2)] reacts with gold(I) salts to yield dimetallic compounds, the molecular structures of which have been determined by X-ray diffraction. Solid cis-[Pt(PN(th))(2)] shows vapoluminescent properties if exposed to alcohol vapors. A combined photophysical and crystallographic investigation has been carried out to clarify the unprecedented rigidochromic role of the alcohol in this phenomenon.     

Halo-carbonyl complexes of palladium,platinum and gold

In this review we summarize some recent literature data concerning synthetic procedures, properties, structure, reactivity and applications of halo-carbonyl complexes of palladium, platinum and gold, taking into consideration that the organometallic chemistry of these metals, with a particular attention to the halo-carbonyls, has been reviewed 20 years ago [F. Calderazzo, J. Organomet. Chem. 400 (1990) 303]. A brief overview of the early studies is provided.     

Design,synthesis and in vitro cytotoxicity of novel dinuclear platinum(II) complexes with a tetradentate carrier ligand

Four novel dinuclear platinum complexes with a tetradentate ligand, (1R,1′R,2R,2′R)‐N¹,N^1′‐(1,2‐phenylenebis(methylene))dicyclohexane‐1,2‐diamine, as the carrier group, have been designed, synthesized and characterized, and their in vitro cytotoxicity against HepG‐2, A549, HCT‐116 and MCF‐7 cell lines evaluated using MTT assay. Results indicate that the targeted dinuclear platinum complexes H1 , H2 , H3 , H4 exhibit significant growth inhibitory properties against HepG‐2, A549 and HCT‐116 cell lines, but none of them show activity against MCF‐7 cell line. Compound H4 shows better antitumor activity than carboplatin against HepG‐2, A549 and HCT‐116 cell lines. Copyright © 2015 John Wiley & Sons, Ltd.     

New dinuclear palladium complex with a Chinese-lantern structure

The new dinuclear palladium complex Pd₂(-S,N-SC₇H₅N₂)₄ with a Chinese-lantern structure was synthesized by the reaction of K₂PdCl₄ with 2-mercaptobenzimidazole and structurally characterized by X-ray diffraction analysis.     

Unsymmetrical, oxazolinyl-containing achiral and chiral NCN pincer ligand precursors and their complexes with palladium(II)

The unsymmetrical, achiral and chiral NCN pincer ligand precursors (3a-3d) with oxazoline and pyrazole as N donors as well as (3e) which has oxazolinyl and amino group have been synthesized in a facile manner in four steps starting from commercially available isophthalaldehyde. Direct C2 metallation of the precursors (3a-3e) with Pd(OAc)₂ in refluxing HOAc, followed by treatment with LiCl at room temperature provided convenient access to the corresponding pincer palladium(II) complexes (4a-4e). The molecular structure of complex 4e has been determined by X-ray single-crystal diffraction. The obtained Pd complexes exhibited good activities in the Suzuki reactions of aryl bromides and activated aryl chlorides with phenylboronic acid.     

Mesomorphic behaviour and TSDC measurements of ortho-metallated palladium(II) and platinum(II) complexes with S,O-donor co-ligands

A series of ortho-metallated Pd and Pt complexes containing an imine ligand carrying three alkoxy chains and N-benzoylthiourea derivatives as co-ligands were prepared and their liquid crystalline properties investigated. Their structures were assigned based on elemental analysis, IR and ¹H NMR spectroscopy, whereas thermal properties were investigated by differential scanning calotimetry and polarising optical microscopy. All the compounds exhibit monotropic transitions involving nematic and smectic A phases, with the mesomorphic behaviour strongly related to the type of N-benzoylthiourea as well as the metal centre used. The thermally stimulated depolarisation current technique was employed to determine the conduction mechanism, phase transition temperature and the activation energies for one of the ortho-metallated Pd complexes.     

Hydrogen bonds and protonation of carbonyl-containing polynuclear rhodium complexes

According to IR spectroscopy data, the interaction of bi-, tri-, and tetranuclear cyclopentadienylcarbonyl rhodium complexes with rather weak protic acids (phenols, fluoroalcohols) in low-polarity media results in the formation of hydrogen bonds of the OH...O=C type with bridged carbonyl groups. According to¹H NMR data, protonation of these complexes with strong acids (CF₃COOH and HBF₄) occurs at the the Rh-Rh bond to give the symmetrical bridge.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 386–388, February, 1995.This work was carried out with the financial support of the Russian Foundation for Basic Research (Project No. 93-03-0461).     

Air-stable platinum and palladium complexes featuring bis[2,4-bis(trifluoromethyl)phenyl]phosphinous acid ligands

Secondary phosphane oxides, R(2)P(O)H, are commonly used as preligands for transition-metal complexes of phosphinous acids, R(2)P-OH (R=alkyl, aryl), which are relevant as efficient catalysts in cross-coupling processes. In contrast to previous work by other groups, we are interested in the ligating properties of an electron-deficient phosphinous acid, (R(f))(2)P-OH, bearing the strongly electron-withdrawing and sterically demanding 2,4-bis(trifluoromethyl)phenyl group towards catalysis-relevant metals, such as palladium and platinum. The preligand bis[2,4-bis(trifluoromethyl)phenyl]phosphane oxide, (R(f))(2)P(O)H, reacts smoothly with solid platinum(II) dichloride yielding the trans-configured phosphinous acid platinum complex trans-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)]. The deprotonation of one phosphinous acid ligand with an appropriate base leads to the cis-configured monoanion complex cis-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H](-), featuring the quasi-chelating phosphinous acid phosphinito unit, (R(f))(2)P-O-H···O=P(R(f))(2), which exhibits a strong hydrogen bridge substantiated by an O···O distance of 245.1(4) pm. The second deprotonation step is accompanied by a rearrangement to afford the trans-configured dianion trans-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)](2-). The reaction of (R(f))(2)P(O)H with solid palladium(II) dichloride initially yields a mononuclear palladium complex [PdCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)], which condenses under liberation of HCl to the neutral dinuclear palladium complex [Pd(2)(μ-Cl)(2){({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H}(2)]. The equilibrium between the mononuclear [PdCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)] and dinuclear [Pd(2)(μ-Cl)(2){({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H}(2)] palladium complexes is reversible and can be shifted in each direction by the addition of base or HCl, respectively. Treatment of palladium(II) hexafluoroacetylacetonate, [Pd(F(6)acac)(2)], with a slight excess of (R(f))(2)P(O)H yields the complex [Pd(F(6)acac)({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H]. The quasi-chelating phosphinous acid phosphinito unit, which is formed by the liberation of HF(6)acac, is characterized by a O···O distance of 244.1(3) pm. These transition metal complexes are stable towards air and moisture and can be stored for months without any evidence of decomposition.