Reactions of Dinitrogentrioxide with Rhodium(I) Complexes and with Rhodiumtrichloride trihydrate in presence of triphenylphosphine and triphenylarsine

Dinitrogen-trioxide reacts with rhodium(I) complexes and with rhodium trichloride trihydrated in presence of triphenylphosphine and triphenylarsine to give rhodium(III) nitrosylnitro complexes and rhodium(III) nitrosyl complexes which are characterized by ir spectra, magnetic measurement and elemental analyses.     

超痕量铑的催化动力学分析研究

在氯化钠存在的磷酸介质中，铑（Ⅲ）对高碘酸钾氧化罗丹明Ｂ裉色的反应具有强烈的催化作用，该催化反应对罗丹明Ｂ和铑（Ⅲ）均为一级反应，反应的表观活化能为６８．３８ｋＪ／ｍｏｌ。以该反应为指示反应建立的动力学光度法可测定０．０３－２．５ｎｇ／２５ｍｌ的铑，考察了３０多种离子的干扰情况，本法选择性好。     

When is a nanoparticle a cluster? An operando EXAFS study of amine borane dehydrocoupling by Rh(4-6) clusters

X-ray absorption fine structure (XAFS) is used to determine the structure of the rhodium cluster present during the catalyzed dehydrocoupling of amine boranes under operando conditions. We show how a variety of XAFS strategies can be used in combination with other analytical methods to differentiate homogeneous from heterogeneous systems. Analysis of the in situ XAFS spectra using a series of amine boranes (NH3BH3, R2NHBH3, and RNH2BH3 where R = methyl, isopropyl, tert-butyl, and cyclohexyl) and rhodium catalyst precursor compounds (including chloro-(1,5-cyclooctadiene)rhodium (I) dimer, bis(1,5-cyclooctadiene)rhodium (I) trifluoromethanesulfonate, chlorodicarbonylrhodium (I) dimer, dichloro(pentamethylcylcopentadienyl)rhodium (III) dimer, hexarhodium hexadecacarbonyl, and tetrarhodium dodecacarbonyl) strongly suggest that the active catalyst species for this reaction is a homogeneous rhodium complex. Rhodium clusters containing four or six rhodium atoms (Rh(4-6)) bound to amine boranes are observed as the major (>99%) rhodium containing species during and after the catalyzed anaerobic dehydrocoupling. During the later stages of the reaction a nonmetallic rhodium complex precipitates in which individual Rh(4-6) clusters likely form polymer chains ligated by the reaction products that have two or more ligating sites. The best fits of the XAFS data, using ab initio calculations of FEFF theory, show that the major rhodium species (80%) has each rhodium atom directly bound to three rhodium atoms with an observed bond distance of 2.73 A and to two boron atoms at 2.10 A. A minor (20%) rhodium species has each rhodium atom bound to four rhodium atoms with a bond distance of about 2.73 A and a single rhodium atom at a nonbonding distance of 3.88 A. No metallic rhodium was observed at any time during the anaerobic reaction.     

Studies on optimization of conditions for separating rhodium and platinum by cation-exchange

It has been established that, owing to the amphoteric properties of rhodium(III) hydroxide, by making a rhodium chloride solution alkaline (pH approximately 13) with sodium hydroxide and then acidifying to pH 2 with nitric acid it is possible to convert at least 99% of the rhodium into cationic forms. This fact is utilized for separation of rhodium(III) and platinum(IV) from chloride solutions on a sulphonic acid cation-exchanger in hydrogen form. Loss of rhodium in the separation process is < 1%. Platinum elution is complete. This method is suitable for separation of mixtures of rhodium and platinum (present in molar ratio between 1:200 and 20:1).     

Preparation of Colloidal Rhodium in Poly(vinyl Alcohol) by Reduction with Methanol

Refluxing of a solution of poly(vinyl alcohol) and rhodium(III) chloride in methanol-water gives a colloidal dispersion of rhodium which is an effective catalyst for hydrogenation of cyclohexene in methanol at 30°C under atmospheric hydrogen pressure. Formaldehyde is produced quantitatively with the reduction of rhodium(III) chloride to metallic rhodium. The rhodium particles in the colloidal dispersion are found to consist of two kinds of particles, about 8 and 40 Å in diameter by electron microscopy. The sizes of the small (8 Å) and large (40 Å) particles are almost constant during the course of refluxing. The number of small particles, which is the great majority of particles at the early stage of refluxing, gradually decreases; concurrently the number of large particle increases on prolonged refluxing. An absorption peak appears at 260 nm at the early stage of refluxing. The presence of the 260 nm peak, which indicates the coordination of poly(vinyl alcohol) to rhodium(III) ion, is indispensable for the formation of a homogeneous colloidal dispersion of rhodium. The addition of ethylenediamine inhibits the formation of colloidal rhodium in refluxing. The catalytic activity of colloidal dispersion of rhodium is dependent upon the concentration of rhodium(III) chloride charged and is independent of that of poly(vinyl alcohol). The formation mechanism of colloidal rhodium is discussed.     

Reaction of nitrosyltribromide with rhodium(I) complexes and with rhodiumtrichloride trihydrate,in the presence of triphenylphosphine and triphenylarsine

Summary Nitrosyltribromide reacts with rhodium(I) complexes and with rhodiumtrichloride trihydrate in the presence of triphenylphosphine and triphenylarsine to give rhodium(III) nitrosyl complexes and rhodium(III) hyponitrite complexes which are characterized by i.r. spectra, magnetic measurements and by elemental analyses.     

Design and Synthesis of Isocyanide Ligands for Catalysis: Application to Rh‐Catalyzed Hydrosilylation of Ketones

New isocyanide ligands with meta‐terphenyl backbones were synthesized. 2,6‐Bis[3,5‐bis(trimethylsilyl)phenyl]‐4‐methylphenyl isocyanide exhibited the highest rate acceleration in rhodium‐catalyzed hydrosilylation among other isocyanide and phosphine ligands tested in this study. ¹H NMR spectroscopic studies on the coordination behavior of the new ligands to [Rh(cod)₂]BF₄ indicated that 2,6‐bis[3,5‐bis(trimethylsilyl)phenyl]‐4‐methylphenyl isocyanide exclusively forms the biscoordinated rhodium–isocyanide complex, whereas less sterically demanding isocyanide ligands predominantly form tetracoordinated rhodium–isocyanide complexes. FTIR and ¹³C NMR spectroscopic studies on the hydrosilylation reaction mixture with the rhodium–isocyanide catalyst showed that the major catalytic species responsible for the hydrosilylation activity is the Rh complex coordinated with the isocyanide ligand. DFT calculations of model compounds revealed the higher affinity of isocyanides for rhodium relative to phosphines. The combined effect of high ligand affinity for the rhodium atom and the bulkiness of the ligand, which facilitates the formation of a catalytically active, monoisocyanide–rhodium species, is proposed to account for the catalytic efficiency of the rhodium–bulky isocyanide system in hydrosilylation.     

Rhodium-catalyzed arylative and alkenylative cyclization of 1,5-enynes induced by geminal carbometalation of alkynes

A rhodium(I)-catalyzed addition-cyclization of 1,5-enynes with aryl- and alkenylboronic acids has been developed. The reaction allows for efficient C-C coupling of multiple reactive components while accomplishing a net R,H-addition in a single step under mild conditions. In the presence of [Rh(OH)(COD)]2 catalyst and triethylamine base in methanol solvent, a range of 1,5-enynes undergo an intermolecular addition with a wide variety of aryl- and alkenylboronic acids and concomitant endo-selective cyclization to yield 1-aryl and alkenyl-substituted cyclopentene derivatives as the products. Deuterium labeling studies suggest that the reaction involves formation of a rhodium vinylidene complex with the terminal alkyne of the enyne substrate. The subsequent migration of the aryl or alkenyl group from the rhodium center to the alpha-carbon of the vinylidene ligand gives a vinyl rhodium complex, a formal 1,1-carbometalation process of the alkyne. This vinyl rhodium then adds to the pendent alkene, and the protodemetalation of the resulting rhodium enolate affords the product.     

湿法消解-电感耦合等离子体原子发射光谱(ICP-AES)法测定含铑废催化剂冶金废水中铑

摘 要：建立了硫酸、过氧化氢湿法消解、ICP-AES测定铑派克洗水铑的含量的分析方法。确定了硫酸碳化有机物,过氧化氢溶解煮沸,氢氟酸除硅,于4mol/L盐酸体系,碲共沉淀富集铑,10%盐酸介质,电感耦合等离子体发射光谱仪测定铑量。在选定条件下,测定含铑有机物洗水中0.0003 g/L～0.010 g/L的铑,相对标准偏差（RSD,n=7）和加标回收率分别为：铑0.545%～2.91%和99.62%%～100.55%。。方法准确、快速、简便,测定结果与火试金富集分析方法结果吻合。     

Determination of acid-soluble and total rhodium on alumina-supported catalysts

Characterization of alumina-supported catalysts required determination of rhodium by atomic-absorption spectroscopy (AAS). Catalysts were loaded with 0.1-2.0% rhodium chloride and calcined at 400 degrees . Rhodium remaining as the chloride was regarded as the soluble form, while that converted into the oxide or bonded to the alumina was regarded as the bonded form. By selective dissolution procedures, soluble rhodium was leached from the substrate and determined by AAS. Total rhodium was determined after the catalyst had been fused with sodium peroxide. Bonded rhodium can be determined by difference or by analysing leached residue. Optimization of AAS conditions, use of spectroscopic buffer solution and elimination of interelement interferences are discussed.     

Rhodium‐Mediated Oxygenation of Nitriles with Dioxygen: Isolation of Rhodium Derivatives of Peroxyimidic Acids

Dioxygen is used as the oxygenation agent in the rhodium‐mediated conversion of nitriles into amides. The characterization of intermediate species and model compounds as well as isotope‐labeling studies provided an insight into the reaction mechanism. The conversions of rhodium hydroperoxido or methylperoxido complexes with nitriles into metallacyclic rhodium‐ κ²‐(N,O)‐peroxyimidate compounds represent essential key steps. The former are accessible from a rhodium(III) peroxido complex and the latter represent rhodium derivatives of Payne’s reagent (peroxyimidic acids).     

Determination of rhodium in waters by Mg-W cell-electrodeposition and electrothermal atomic absorption spectrometry

A new concentration method of rhodium using Mg-W cell-electrodeposition has been developed. The method was combined with electrothermal atomic absorption spectrometry (ETAAS) with a tungsten tube atomizer. The optimal immersing time was 120 s. The most suitable pH for rhodium electrodeposition was 1.0. Under optimal conditions, the detection limit of rhodium by the ETAAS with the preconcentration was 13 ng ml(-1) (3S/N). The severe interferences on the AAS signal of rhodium by large amounts of Ca, Cu, Fe, K, Na, Pb and Zn were eliminated by the Mg-W cell-electrodeposition method. The method was applied to the determination of rhodium in river and sea water. The recovery of rhodium spiked environmental samples was in the range of 95.6-109%. The present Mg-W cell-electrodeposition method can be utilized in in-situ sampling of trace elements in environmental samples (water). Furthermore, after sampling, it is easy to carry and store the W-sheet without contamination for a long time.     

Synthesis and reactions of rhodium compounds containing tellurium donor ligands

This paper describes the synthesis and characterization of a series of rhodium(I) and rhodium(III) complexes containing tellurium-rhodium bonds resulting from the coordination of diorgano telluride or organotelluro ligands. Oxidative addition, metathesis and substitution reactions of these compounds have been examined, and the resulting products are compared with those from the known reactions of rhodium(I) and rhodium(III) compounds containing phosphine ligands.     

Separation of trace amounts of rhodium(III) with tri-n-butyl phosphate from nitric acid and sodium trichloroacetate media

A new method for the quantitative extraction and separation of trace amounts of rhodium from nitric acid and sodium trichloroacetate media has been established based on the formation of an ion-association complex of hexahydrated rhodium cation Rh(H₂O)₆ ³⁺ and the trichloroacetate (TCA) anion in tri-n-butyl phosphate (TBP). The effect of various factors (solvent, pH, sodium trichloroacetate, shaking time, phase volume ratio, composition of the extracted species, foreign ions, transformation of rhodium chlorocomplexes into hexahydrated cation, etc.) on the extraction and back-extraction of rhodium has been investigated. The method can be combined with subsequent FAAS determination of rhodium. The procedure was applied to determine rhodium traces in chloroplatinic acid and palladium chloride. Received: 17 March 2000 / Revised: 15 May 2000 / Accepted: 19 May 2000     

Hydroformylation activity of multinuclear rhodium complexes coordinated to dendritic iminopyridyl and iminophosphine scaffolds

The synthesis of poly(propyleneimine)-iminopyridyl and iminophosphine rhodium(I) metallodendrimers, with rhodium coordinated to monodentate (N-donor) and chelating, heterobidentate (P,N) moieties respectively located on the periphery, has been accomplished in order to evaluate their potential as hydroformylation catalysts. Related mononuclear complexes were obtained in a similar manner to model the multinuclear complexes. The multinuclear rhodium(I) complexes were found to be effective catalyst precursors in the hydroformylation of 1-octene, achieving higher conversions, faster reaction rates and slightly enhanced catalytic activity when compared with analogous mononuclear rhodium complexes. Hydroformylation reactions using the tetra- and octanuclear rhodium complexes generally show a chemoselective formation of aldehydes, together with a small amount of isomerisation products.     

Asymmetric Alkenylation of Enones and Imines Enabled by A Highly Efficient Aryl to Vinyl 1,4‐Rhodium Migration

The asymmetric rhodium‐catalyzed alkenylation of enones and imines with arylboronic acids has been developed. A highly controllable aryl to vinyl 1,4‐rhodium migration is the key step. Stereodefined vinyl moieties were installed in excellent enantioselectivies for most examined examples. DFT calculations reveal that the driving force of this rhodium migration is a kinetically favored process.     

Activation of aliphatic carbon-carbon bonds of esters and amides by rhodium(II) porphyrin

Aliphatic carbon-carbon bonds of esters and amides were activated successfully with rhodium(II) porphyrin radical to give rhodium(III) porphyrin alkyls in moderate yields.     

Electrocrystallization of rhodium clusters on thiolate-covered polycrystalline gold

This study reports on the electrochemical deposition of rhodium metal clusters on a polycrystalline gold electrode, modified with a monolayer of dodecanethiol through self-assembly from solution. The deposition process was investigated using cyclic voltammetry, chronoamperometry, and electrochemical quartz crystal microbalance. It is shown that the presence of the thiol monolayer drastically alters the nucleation and growth mechanism compared with the mechanism on the bare gold electrode. The small uncovered gold domains, located at the imperfections in the thiolate monolayer which are induced by the gold nanoroughness, act as nucleation sites for small rhodium clusters. At longer times, these clusters can outgrow the organic monolayer. The resulting surface morphology was characterized by scanning electron microscopy. Rhodium electrocrystallization on the bare gold substrate resulted in an ensemble of a very large amount of very small clusters that are difficult to distinguish from the gold roughness. In contrast, in the presence of a self-assembled monolayer (SAM) of dodecanethiol covalently attached to the gold electrode, the resulting deposit consisted of an ensemble of hemispherical particles. The size distribution of the rhodium particles obtained by using double step chronoamperometry was compared to the ones obtained with cyclic voltammetry and "classical" chronoamperometry. It is shown by X-ray photoelectron spectroscopy that the SAM is still present after rhodium deposition on the thiolate-covered gold substrate. Because the rhodium clusters are directly attached to the gold substrate and can thus easily be electrified, the resulting interface could be used as a composite electrode consisting of a random array of gold supported rhodium nano/microparticles separated from each other by an organic phase. On the other hand, it is shown that the SAM is easily removed by electrochemical oxidation without dissolving the rhodium clusters and, thus, leaving a different array of rhodium clusters on the gold surface compared with the topography obtained in the absence of the SAM. From this point of view, substrate modification with such "removable" organic monolayers was found to be an interesting tool to tune the nano- or microtopography of electrochemically deposited rhodium.     

Carbon-nitrogen bond activation of amines by rhodium(III) porphyrin complexes

Carbon-nitrogen bond activation of amines by rhodium porphyrin chloride has been achieved to give rhodium porphyrin alkyl complexes. Rhodium porphyrin hydride and rhodium porphyrin dimer were proposed as the intermediates in cleaving the C-N bond.     

Catalyst and substituent effects on the rhodium(II)-catalysed intramolecular Buchner reaction

Intramolecular rhodium(II)-catalysed aromatic addition (Buchner) reactions of a range of α- and β-substituted α-diazoketones are reported. Both steric and electronic effects are evident for the aromatic additions investigated. In general, highly efficient aromatic addition is achieved through use of rhodium carboxylates bearing electronegative ligands, such as rhodium trifluoroacetate, while aromatic addition employing rhodium catalysts with more electron-donating ligands, such as rhodium caprolactam, is less efficient. Excellent levels of diastereoselectivity are possible for this process in the presence of rhodium acetate and rhodium caprolactam, however, a reduction in diastereocontrol is generally associated with use of the more reactive, electronegative catalysts. Interestingly, these catalyst effects can be overcome through the steric effects of the substituents on the α-diazoketone substrates, with the presence of sterically bulky substituents at the 2- or 3-position rendering the aromatic addition essentially catalyst independent in terms of efficiency and diastereocontrol.