Ethyltetramethylcyclopentadienyl complexes of cobalt,rhodium, iridium and ruthenium

Summary The syntheses of the ethyltetramethylcyclopentadienyl complexes Ru(⁵-C₅Me₄Et)(CO)₂Cl, CO( ⁵-C₅Me₄Et)(CO)₂, and [M( ⁵-C₅Me₄Et)Cl₂]₂ (M = Rh or Ir) are described; the ruthenium complex reacts with triphenylarsine to give Ru( ⁵-C₅Me₄Et)(AsPh₃)(CO)Cl.¹H and¹³C n.m.r. spectra, i.r. spectra and the physical properties of the compounds are discussed and contrasted with the known C₅H₅ and C₅Me₅ analogues.     

Solvent extraction of rhodium,ruthenium, and iridium with HDEHP

Solvent extraction of rhodium, ruthenium, and iridium with HDEHP from thioureachloride media was investigated. Under the conditions ([Cl^–]=0.50 M, [HDEHP]=1.0M, [SC(NH₂)₂]=0.50M, pH=4.50, phase contact time 1 min), Rh(III) is extracted 88.3%, Ru(III) and Ir(III) 40.8% and 28.5% respectively at phase ratio 11. The formation of rhodium-thiourea complexes in aqueous solutions, even at 5M chloride concentration, with the possible composition Rh[SC (NH₂)₂]₆ ³⁺ is confirmed by the observed molar ratio of thiourea to rhodium and UV-spectra.     

Reaction of sulphur dioxide with chlorocarbonyls of ruthenium,rhodium and iridium

Summary The reactions of SO₂ with chlorocarbonyls of rhodium and iridium ([M(CO)₂Cl₂]^– and ruthenium ([Ru(CO)_2–Cl₂]_n) ions were studied. Addition of either the Ph₄As⁺ cation or the nitrogen-donor ligands 2,2-bipyridine (bipy),o-phenylenediamine (opd), 1,10-phenanthroline (phen), 2,2,6,2-terpyridine (terpy) or 6,7-dihydro-1,4-di(2-pyridyl)-5H-cyclopenta {d}-pyridazine (5-dppn) to the SO_2– treated chlorocarbonyl solutions resulted in the formation of various complexes according to the nature of metal and ligand. The products have been characterized by physicochemical methods.     

The coordination chemistry and reactivity of amino-dithiaphospholanes with rhodium, iridium, and ruthenium

Novel amino-dithiaphospholane complexes of ruthenium, iridium, and rhodium were synthesized, and their properties were studied. Reaction of the new amino-dithiaphospholane (RS)₂ (R = binaphthyl, R′ = CH₂Ph, (rac)-4) with [RuCl₂(p-cymene)]₂ afforded [RuCl₂(p-cymene)((rac)-4)] in 67% isolated yield. Similarly, the new amino-dithiaphospholanes (RS)₂ (R = cyclohexyl, (rac)-7) and (RS)₂ (R = phenyl, 9) gave upon reaction with [RhCl(CO)₂]₂ and [IrCp^∗Cl₂]₂ the novel complexes [RhCl(CO)(L)₂] and [IrCp^∗Cl₂(L)] (L = (rac)-7, 9) in 61-96% yields. The ruthenium complex is catalytically active for the etherification of propargylic alcohols with methanol and ethanol (8-48 h, 90 °C, 40-85% isolated yields).     

C-H Activation by dinuclear phosphine bridged complexes of rhodium,iridium, and ruthenium

The possibility of activation of the C-H bond by dinuclear phosphine bridged complexes of rhodium, iridium, and ruthenium is considered.This work was reported at the conference Modern Problems of Organometallic Chemistry (8–13 May, 1994, Moscow).Institut fer Technische Chemie und Petrolchemie der RWTH Aachen Worringerweg 1, 52074 Aachen, Deutschland.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 589–593, April, 1994.     

Dicarba-closo-dodecarborane-containing half-sandwich complexes of ruthenium, osmium, rhodium and iridium: biological relevance and synthetic strategies

This review describes how the incorporation of dicarba-closo-dodecarboranes into half-sandwich complexes of ruthenium, osmium, rhodium and iridium might lead to the development of a new class of compounds with applications in medicine. Such a combination not only has unexplored potential in traditional areas such as Boron Neutron Capture Therapy agents, but also as pharmacophores for the targeting of biologically important proteins and the development of targeted drugs. The synthetic pathways used for the syntheses of dicarba-closo-dodecarboranes-containing half-sandwich complexes of ruthenium, osmium, rhodium and iridium are also reviewed. Complexes with a wide variety of geometries and characteristics can be prepared. Examples of addition reactions on the metal centre, B-H activation, transmetalation reactions and/or direct formation of metal-metal bonds are discussed (103 references).     

Synthesis and cytotoxicity of methyl-substituted 8-quinolineselenolates of ruthenium,rhodium, osmium,and iridium

A series of 2-methyl, 4-methyl, and 2,4-dimethyl-8-quinolineselenolates of ruthenium, rhodium, osmium, and iridium has been synthesized and their cytotoxicity towards HT-1080 (human fibrosarcoma) and MG-22A (mouse hepatoma) tumor cells studied. It was found that all of the osmium complexes had a high cytotoxicity towards both cell lines. Their toxicity towards the normal mouse embryonic fibroblasts NIH-3T3 depends on the position and number of methyl groups in the quinoline ring and decreases in the order 2-Me > 4-Me > 2,4-Me₂. The greatest selectivity in cytoxic activity is noted for iridium 4-methyl-8-quinolineselenolate and ruthenium 2-methyl-8-quinolineselenolate. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 230–236, February, 2009.     

The coordination chemistry of simple phospholes. Complexes of rhenium,ruthenium, cobalt,rhodium and iridium chlorides and of some chlorocarbonyls of ruthenium and rhodium

The reactions of 1-phenylphosphole (PP), 3-methyl-1-phenylphosphole (mPP), 3,4-dimethyl-1-phenylphosphole (dPP) and, in certain instances, 1-n-butyl-3,4-dimethylphosphole (dBP) with some transition metal chlorides and some metal-Cl-CO systems are reported. These reactions show that simple phospholes in general unexpectedly behave much like ordinary tertiary phosphines and that, unlike the reactions with Ni(II), Pd(II) and Pt(II), the complexes formed are conventional in most respects. However, a few unusual reactions were observed. For example, mPP partially reduces Ru(III) to give a mixed-valent Ru(III)-Ru(II) complex while PP reduces Ir(III) to Ir(I). From infrared spectroscopic studies of the square-planar Rh(I) complexes L₂Rh(CO) Cl (L = phosphole), it appears that donor character decreases with decreasing substitution on the phosphole ring carbon atoms. Phosphorus-phenyl cleavage has been observed in reactions of 1-phenylphosphole with Rh-CO systems. The results are briefly discussed in relation to the behaviour of other phospholes in similar reactions and in the context of the electronic structure of phospholes.     

Some examples of unusual skeletal bonding topologies in metallaboranes containing two or three early transition metal vertices

The metallaboranes (CpM)(2)B(n)H(n+4) (M = Cr, Mo, W; n = 4, 5; Cp = eta(5)-C(5)H(5), eta(5)-C(5)Me(5)), (CpW)(2)B(7)H(9), (CpRe)(2)B(7)H(7), and (CpW)(3)B(8)H(9) have the 2v or 2v + 2 skeletal electrons for closo or isocloso deltahedra (v = number of polyhedral vertices) if the early transition metal vertices are assumed to contribute four or more internal orbitals rather than the usual three internal orbitals for BH vertices. The polyhedra for the metallaboranes (CpM)(2)B(n)H(n+4) (M = Cr, Mo, W; n = 4, 5) are derived from (n + 1)-gonal bipyramids by removal of an equatorial vertex. The deltahedra for the larger metallaboranes (CpW)(2)B(7)H(9), (CpRe)(2)B(7)H(7), and (CpW)(3)B(8)H(9) are derived from the corresponding B(n)H(n)(2)(-) deltahedra (n = 9 and 11 in these cases) by sufficient diamond-square-diamond processes to provide vertices of degrees > or = 6 for each of the CpM vertices. Reasonable skeletal bonding topologies in accord with the availability of skeletal electrons and orbitals consist of surface 2c-2e and 3c-2e bonds supplemented by metal-metal bonding through the center of the polyhedron.     

Oblate deltahedra in dimetallaboranes: geometry and chemical bonding

A new series of nonspherical and very oblate deltahedra, conveniently called the oblatocloso deltahedra, is found in dimetallaboranes among which the dirhenaboranes Cp2Re2B(n-2)H(n-2) (8 相似文献   

The scope of ambiphilic acetate-assisted cyclometallation with half-sandwich complexes of iridium, rhodium and ruthenium

C? H activation by acetate‐assisted cyclometallation of a phenyl group with half‐sandwich complexes [{MCl₂Cp*}₂] (M=Ir, Rh) and [{RuCl₂(p‐cymene)}₂] can be directed by a wide range of nitrogen donor ligands including pyrazole, oxazoline, oxime, imidazole and triazole, and X‐ray structures of a number of complexes are reported. All the ligands tested cyclometallated at iridium, however ruthenium and rhodium fail to cause cyclometallation in some cases. As a result, the nitrogen donors have been categorised based on their reactivity with the three metals used. The relevance of these cyclometallation reactions to catalytic synthesis of carbocycles and heterocycles is discussed.     

Separation of rhodium from ruthenium and iridium by fast solvent extraction with HDEHP

Solvent extraction of rhodium, ruthenium and iridium with di(2-ethylhexyl)phosphoric acid (HDEHP) has been investigated. Under the conditions [Cl^–1]=0.20M, [(HDEHP)₂]=0.30M, pH 4.05, phase contact time 1 minutes, Rh(III) is extracted 90.7%, Ru(III) and Ir(III) 20.0% and 11.5%, respectively, at phase ratio 11. The distribution ratio of rhodium is proportional to [(HDEHP)₂]³ for a freshly prepared aqueous phase with low chloride concentration but might drop to [(HDEHP)₂]^1to2 for an aqueous phase high in chloride concentration and after standing. The spectroscopic studies indicate that the extracted compound of rhodium is Rh(H₂O)_6–x Cl _x [H(DEHP)₂]_3–x (x=0, 1, 2).     

Complexes of platinum,rhodium, iridium and ruthenium with a thiosemicarbazone derived from thiophene-2-carboxaldehyde

Summary Complexes of thiophene-2-carboxaldehyde thiosemicarbazone with Ru^III, Rh^III, Ir^III and Pt^IV have been prepared and characterized by elemental analyses, molar conductance, room temperature, magnetic moments, infrared and electronic spectral studies. Probable structures for the complexes are suggested. All are diamagnetic except the Ru^III complexes and possess octahedral structures. The crystal field parameters of the complexes have also been calculated.     

Preparation, structure, and ethylene polymerization behavior of half-sandwich picolyl-functionalized carborane iridium, ruthenium, and rhodium complexes

The synthesis of half-sandwich transition-metal complexes containing the Cab(N) and Cab(N,S) chelate ligands (HCab(N) = HC2B10H10CH2C5H4N (1), LiCab(N,S) = LiSC2B10H10CH2C5H4N (4)) is described. Compounds 1 and 4 were treated with chloride-bridged dimers [{Ir(Cp*)Cl2}2] (Cp* = eta5-C5Me5), [{Ru(p-cymene)Cl2}2] and [{Rh(Cp*)Cl2}2] to give half-sandwich complexes [Ir(Cp*)Cl(Cab(N))] (2), [Ru(p-cymene)Cl(Cab(N))] (3), and [Rh(Cp*)Cl(Cab(N,S))] (5), respectively. Addition reaction of LiCab(S) (Cab(S) = SC2(H)B10H10) to the rhodium complex 5 yields [Rh(Cp*)(Cab(S))(Cab(N,S))] (6). All the complexes were characterized by IR and NMR spectroscopy, and by elemental analysis. In addition, X-ray structure analyses were performed on complexes 2, 3, 5, and 6, in which the potential C,N- and N,S-chelate ligands were found to coordinate in a bidentate mode. The carborane complex 2 shows catalytic activities up to 3.7x10(5) g PE mol(-1) Ir h(-1) for the polymerization of ethylene in the presence of methylaluminoxane (MAO) as cocatalyst. The polymer obtained from this homogeneous catalytic reaction has a spherical morphology. Catalytic activities and the molecular weight of polyethylene have been investigated for various reaction conditions.     

Mono and dinuclear iridium, rhodium and ruthenium complexes containing chelating carboxylato pyrazine ligands: Synthesis, molecular structure and electrochemistry

The mononuclear complexes [(η⁵-C₅Me₅)IrCl(L¹)] (1), [(η⁵-C₅Me₅)RhCl(L¹)] (2), [(η⁶-p-PrⁱC₆H₄Me)RuCl(L¹)] (3) and [(η⁶-C₆Me₆)RuCl(L¹)] (4) have been synthesised from pyrazine-2-carboxylic acid (HL¹) and the corresponding complexes [{(η⁵-C₅Me₅)IrCl₂}₂], [{(η⁵-C₅Me₅)RhCl₂}₂], [{(η⁶-p-PrⁱC₆H₄Me)RuCl₂}₂], and [{(η⁶-C₆Me₆)RuCl₂}₂], respectively. The related dinuclear complexes [{(η⁵-C₅Me₅)IrCl}₂(μ-L²)] (5), [{(η⁵-C₅Me₅)RhCl}₂(μ-L²)] (6), [{(η⁶-p-PrⁱC₆H₄Me)RuCl}₂(μ-L²)] (7) and [{(η⁶-C₆Me₆)RuCl}₂(μ-L²)] (8) have been obtained in a similar manner from pyrazine-2,5-dicarboxylic acid (H₂L²). Compounds isomeric to the latter series, [{(η⁵-C₅Me₅)IrCl}₂(μ-L³)] (9), [{(η⁵-C₅Me₅)RhCl}₂(μ-L³)] (10), [{(p-PrⁱC₆H₄Me)RuCl}₂(μ-L³)] (11) and [{(η⁶-C₆Me₆)RuCl}₂(μ-L³)] (12), have been prepared by using pyrazine-2,3-dicarboxylic acid (H₂L³) instead of H₂L². The molecular structures of 2 and 3, determined by X-ray diffraction analysis, show the pyrazine-2-carboxylato moiety to act as an N,O-chelating ligand, while the structure analyses of 5-7, confirm that the pyrazine-2,5-dicarboxylato unit bridges two metal centres. The electrochemical behaviour of selected representatives has been studied by voltammetric techniques.     

Graphite furnace atomic absorption spectrometric determination of iridium,rhodium and ruthenium in high-purity platinum after matrix extraction

Ir, Rh and Ru are separated from a large excess of platinum by extraction with isoamyl alcohol-isobutyl methyl ketone mixture. Graphite furnace atomic absorption spectrometry using the method of standard addition is then used to determine the metals with satisfactory precision and accuracy.     

Preparation and structure of mono- and binuclear half-sandwich iridium, ruthenium, and rhodium carbene complexes containing 1,2-dichalcogenolao 1,2-dicarba-closo-dodecaboranes

The synthesis of half-sandwich transition metal complexes containing both 1,2-dichalcogenolato-1,2-dicarba-closo-docecaborane (Cab(E,E)) [Cab(E,E)=E(2)C(2)(B(10)H(10)); E = S, Se] and N-heterocyclic carbene (NHC) ligands is described. Addition of mono-NHC ligand to the 16e half-sandwich dichalcogenolato carborane complexes [Cp*Rh(Cab(E,E))], [Cp*Ir(Cab(S,S))], [(p-cymene)Ru(Cab(S,S))] (Cp* = pentamethylcyclopentadienyl) gives corresponding mononuclear 18e dithiolate complexes of the type [LM(Cab(E,E))(NHC)]: [Cp*M(Cab(S,S))(1-ethenyl-3-methylimidazolin-2-ylidene)] (M = Ir (2), Rh (3)), [Cp*Rh(Cab(E,E))(3-methyl-1-picolyimidazolin-2-ylidene)] [E = S (6), Se (7)], [(p-cymene)Ru(Cab(S,S))(NHC)] [NHC = 1-ethenyl-3-methylimidazolin-2-ylidene (4), 3-methyl-1-picolyimidazolin-2-ylidene (8)], whereas bis-NHC give centrosymmetric binuclear complexes [{Cp*M(Cab(S,S))}(2)(1,1'-dimethyl-3,3'-methylene(imidazolin-2-ylidene))] [M = Rh (10), Ir (11)]. The complexes were characterized by IR, NMR spectroscopy and elemental analysis. In addition, X-ray structure analyses were performed on complexes 2-4, 6, 8, 10 and 11.