Divergent Behavior in the Chemistry of Metal-Bis(dithiolene) Complexes Appended with Peripheral Aliphatic Butyl Chains

Metal-bis(dithiolene) complexes derived from Ni(II), Co(II), Pd(II), Pt(II) and Au(III), bearing butyl aliphatic chains have been synthesized, and fully characterized by a variety of spectroscopic techniques including NMR, UV-vis, IR, HRMS, CV, and X-ray diffraction studies. This comparative study made possible to establish that the Co(II) species appear to be dimeric in the solid state as well as in solution. On the other hand, the coordination complexes based on Ni(II), Pd(II), Pt(II) and Au(III), feature a monomeric structure in both solution and solid state. These metal-bis(dithiolene) complexes are remarkably stable in solution and, in stark contrast to precedents in the literature, they retain their square planar geometry even in presence of pyridine derivatives reported for their apical binding on metal-bis(dithiolene) complexes.     

15N NMR coordination shifts in Pd(II), Pt(II), Au(III), Co(III), Rh(III), Ir(III), Pd(IV), and Pt(IV) complexes with pyridine, 2,2'-bipyridine, 1,10-phenanthroline, quinoline, isoquinoline, 2,2'-biquinoline, 2,2':6', 2'-terpyridine and their alkyl or aryl derivatives

The 15N NMR data for 105 complexes of Pd(II), Pt(II), Au(III), Co(III), Rh(III), Ir(III), Pd(IV), and Pt(IV) complexes with simple azines such as pyridine, 2,2'-bipyridine, 1,10-phenanthroline, quinoline, isoquinoline, 2,2'-biquinoline, 2,2':6', 2'-terpyridine and their alkyl or aryl derivatives have been reviewed. The 15N NMR coordination shifts, i.e. the differences between the 15N chemical shifts of the same nitrogen in the molecules of the complex and the ligand (Delta(15N) (coord) = delta(15N) (compl)--delta(15N) (lig)), have been related to some structural features of the reviewed coordination compounds, like the type of the central ion and the character of auxiliary ligands (mainly in trans position). These Delta(15N) (coord) parameters are negative, their absolute magnitudes (ca 30-150 ppm) generally increasing in the metal order Au(III) < Pd(II) < Pt(II) and Rh(III) < Co(III) < Pt(IV) < Ir(III), as well as with the enhanced trans influence of the other donor atoms (H, C < Cl < N).     

Spectroscopic studies of transition metal complexes with a N-donor tetradentate(N4) 12-membered macrocylic ligand

Chromium(III), manganese(II), iron(III), cobalt(II), nickel(II), copper(II), ruthenium(III), iridium(III), palladium(II) and platinum(II) complexes were synthesized with a 12-membered 1,4,7,10-tetraazadodeca-5,6,11,12-tetraene macrocylic ligand (L) and characterized by elemental analysis, molar conductance, magnetic susceptibility, IR, electronic, EPR and M?ssbauer [Fe(III)] spectral studies. The molar conductance measurements of all the complexes in DMF solution correspond to non-electrolytic nature for M(L)Cl2 complexes [where M=Mn(II), Co(II), Ni(II), Cu(II)], 1:1 electrolytes for M'(L)Cl3 complexes [where M'=Cr(III), Fe(III), Ru(III) and Ir(III)] and 1:2 electrolytes for M'(L)Cl2 complexes [where M'=Pd(II) and Pt(II)]. Thus, the complexes may be formulated as [M(L)C1(2)], [M'(L)C1(2)]C1 and [M'(L)]C1(2), respectively [where L=ligand]. All complexes were of the high-spin type and found to have six-coordinate octahedral geometry except the Pd(II) and Pt(II) complexes which were four coordinate, square planar and diamagnetic.     

Simultaneous determination of gold(III), palladium(II), and platinum(IV) with N-phenyl-N′-(sodium p-aminobenzenesulfonate)thiourea

The preparation and characteristics of a new water-soluble reagent, N-phenyl- N'-(sodium p-aminobenzenesulfonate)thiourea (PPT) are described. In the presence of cetyltrimethylammonium bromide (CTMAB) PPT reacts with Au(III), Pd(II), and Pt(IV) to form colored complexes with absorption maxima at 317 nm, 306.1 nm, 778.4 nm, respectively. Optimum conditions for color development were studied. The reagent was used for the simultaneous determination of Au(III), Pd(II), and Pt(IV); Amberlyst A-26 macropore anion-exchange resin was used as a means of rapid separation. The method was applied to the determination of Au(III), Pd(II), and Pt(IV) in catalyst materials and anode mud with satisfactory results.     

Potentiometric titration and differentiation of cyano and nitrito complexes of Ir(III), Pt(II), and Pd(II)

Summary The precipitation titration of the nitrito complexes of Ir(III), Pt(II), and Pd(II) vs. cetylpyridinium chloride is reported. The corresponding cyanide complexes of these precious metals are also precipitated by silver nitrate, which does not react with the nitrito complexes. Differentiation of the 2 types of complexes is, therefore, possible. Sequential estimation of the cyanide complexes and some anions such as bromide, cyanide, and aurocyanide is feasible with silver nitrate.

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Potentiometrische Titration und Differenzierung von Cyano- und Nitrito-Komplexen von Ir(III), Pt(II) und Pd(II)

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Work performed under the auspices of the U.S. Department of Energy by the Lawrence Livermore National Laboratory under contract number W-7405-ENG-48     

Organophosphorus Ligands in Studies of Metal Complexes. Investigations of Ligand Exchange and Multielement Trace Analysis using Dithiophosphinic Ligands

Abstract

On mixing organic solutions of [Et₂PS₂]M/n and [Prop₂PS₂]M/n [M=Pd(II), Pt(II), Rh(III), lr(III), Cr(III)] an equilibrium is obtained containing statistical amounts of the corresponding mixed ligand complexes as can be shown by 31P{¹H}-NMR, HPLC and FD-MS. With Pt(II)- and Pd(II)-chelates the kinetics of ligand exchange was determined by HPLC. Mixed complexes ML₂L′ and MLL′₂ were isolated from the equilibrium solutions in case of the more inert Cr(III)-, Rh(III)- and lr(III)-chelates by preparative HPLC. Pd(II), Pt(II) and Rh(III) can be determined quickly and simultaneously in aqueous solutions at nanogramm level by complexation with Et₂PS₂? in a modified sample loop followed by reversed phase HPLC.     

Influence of platinum metals on spectral and electrochemical characteristics of metallated azole luminophors

Russian Journal of General Chemistry - Spectral (1H NMR and IR), optical, and voltammetry parameters of Pd(II), Pt(II), Rh(III), and Ir(III) complexes with ethylenediamine and metallated azole...     

Reversed-phase high performance liquid chromatography-spectrophotometry of several platinum group metal complexes with 4-(5-Nitro-2-pyridylazo)resorcinol

The reversed-phase HPLC of several platinum group metal complexes with a new chromogenic reagent 4-(5-nitro-2-pyridylazo)resorcinol (5-NO(2)-PAR) on an ODS column using methanol-ethyl acetate-water (50:10:40, v/v/v) containing 10 mM HAc-NaAc buffer (pH 4.0), 10 mM tetrabutylammonium bromide and 10 mM Na(2)EDTA was investigated. The detection wavelength was 536 nm. Pd(II), Rh(III), Ru(III) and Pt(II) complexes of 5-NO(2)-PAR were separated and determined simultaneously within 18 min. Calibration ranges (ng/ml) were 1.5-500 for Pd(II), 1.5-500 for Rh(III), 2.1-500 for Ru(III) and 7.8-500 for Pt(II). Detection limits were 0.5, 0.5, 0.7 and 2.6 ng/ml, respectively.     

Spectrometric Studies on the Complexation of Pd(II), Fe(III) and Pt(IV) with mandelazo I

Abstract

A spectrometric study of the reaction between Pd(II), Fe(III) and Pt(IV) ions, and Mandelazo I was carried out. The optimum conditions favouring the formation of the complexes are extensively investigated. The stoichiometry of the complexes formed in solution (1:2, 1:1, 1:1), their apparent stability constants (5.45 × 10⁹, 2.39 × 10⁶, 4.12 × 10⁵) and the ranges for obedience to beer's law (0.2 – 6.4, 0.25 – 7.0, 1.5 – 42.0 μg/mL) are reported for Pd(II), Fe(III) and Pt(IV), respectively. The effect of some metal ions including Cu(II), Zn(II), Mn(II), Cd(II), Hg(II), Co(II), Ni(II), Be(II), Al(III), Th(IV) and U(VI), on the maximum absorbance of the formed complexes was also investigated.     

Ion chromatography of chloro complexes of the platinum group metals and gold using bonded phase silica substrates

The ion chromatography of chloro complexes of Au(III), Ir(IV), Ir(III), Os(IV), Pd(II), Pt(IV), Rh(III) and Ru(III) was investigated using anion-exchange and ion-interaction techniques involving silica-based phases. Chloride was either absent or at a very low level and the pH was high enough to enable steel-fabricated liquid chromatography equipment to be used. With anion exchange, Ir(IV), Ir(III), Os(IV) and Pt(IV) gave good stable chromatography and all produced linear calibration plots, except Ir(IV) owing to instability of the sample solution. The detection limits were Ir(III) 5, Os(IV) 10 and Pt(IV) 2 ng ml^?1. The ion-interaction technique was not so successful, only Au(III) and Pd(II) giving stable chromatography. The calibration plots were slightly curved, although acceptable, and the detection limits were 10 and 30 ng ml^?1 for Au (III) and Pd(II), respectively.     

Stereoselective preparation, structures, and reactivities of phosphine-bridged mixed-metal trinuclear and pentanuclear complexes with tris[2-(diphenylphosphino)ethyl]phosphine

The phosphine-bridged linear trinuclear and pentanuclear complexes with Pd(II)-Pt(II)-Pd(II), Ni(II)-Pt(II)-Ni(II), and Rh(III)-Pd(II)-Pt(II)-Pd(II)-Rh(III) metal-ion sequences were almost quantitatively formed by the stepwise phosphine-bridging reaction of the terminal phosphino groups of tris[2-(diphenylphosphino)ethyl]phosphine (pp3), which is the tetradentate bound ligand of the starting Pd(II) and Ni(II) complexes. The solid-state structures of the trinuclear complexes were determined by X-ray structural analyses, and the structures of the polynuclear complexes in solution were characterized by NMR spectroscopy. The trans and cis isomers of the trinuclear and pentanuclear complexes, which arise from the geometry around the Pt(II) center, were selectively obtained simply by changing the counteranion of the starting complexes: the tetrafluoroborate salts, [MX(pp3)](BF4) [M = Pd(II) or Ni(II), X = Cl- or 4-chlorothiophenolate (4-Cltp-)], gave only the trans isomers, and the chloride salt, [PdCl(pp3)]Cl, gave only the cis isomers. The formation of the trinuclear complex with the 4-Cltp- and chloro ligands, trans-[Pt(4-Cltp)2{PdCl(pp3)}2](BF4)2, proceeded with exchange between the thiolato ligand in the starting Pd(II) complex, [Pd(4-Cltp)(pp(3))](BF4), and the chloro ligands in the starting Pt(II) complex, trans-[PtCl2(NCC6H5)2], retaining the trans geometry around the Pt(II) center. In contrast, the formation reaction between [PdCl(pp3)]Cl and trans-[PtCl2(NCC6H5)2] was accompanied by the trans-to-cis geometrical change on the Pt(II) center to give the trinuclear complex, cis-[PtCl2{PdCl(pp3)}2]Cl2. The mechanisms of these structural conversions during the formation reactions were elucidated by the 31P NMR and absorption spectral changes. The differences in the catalytic activity for the Heck reaction were discussed in connection with the bridging structures of the polynuclear complexes in the catalytic cycle.     

Study of the Thermal Decompositions on N,N-Dialkyl-N'-Benzoylthiourea Complexes of Cu(II), Ni(II), Pd(II), Pt(II), Cd(II), Ru(III) and Fe(III)

The thermal decompositions of the complexes of N,N-dialkyl-N'-benzoylthioureas with Cu(II), Ni(II), Pd(II), Pt(II), Cd(II), Ru(III) and Fe(III) were studied by TG and DTA techniques. These metal complexes decompose in two stages: elimination of dialkylbenzamide, and total decomposition to metal sulphides or metals. The influence of the alkyl substituents in these benzoylthiourea chelates on the thermal behaviour of the metal complexes was investigated.This revised version was published online in November 2005 with corrections to the Cover Date.     

Mononuclear transition and non-transition complexes of amlodipine besylate as antihypertensive agent: synthesis,spectral, thermal,and antimicrobial studies

Mononuclear Mn(II), Co(II), Ni(II), Zn(II), Cd(II), Mg(II), Sr(II), Ba(II), Ca(II), Pt(IV), Au(III), and Pd(II) complexes of the drug amlodipine besylate (HL) have been synthesized and characterized by elemental analysis, spectroscopic technique (IR, UV–Vis, solid reflectance, scanning electron microscopy, X-ray powder diffraction, and ¹H-NMR) and magnetic measurements. The elemental analyses of the complexes are confirmed by the stoichiometry of the types [M(HL)(X)₂(H₂O)]·nH₂O [M = Mn(II), Co(II), Zn(II), Ni(II), Mg(II), Sr(II), Ba(II), and Ca(II); X = Cl^? or NO₃ ^?], [Cd(HL)(H₂O)]Cl₂, [Pd(HL)₂]Cl₂, [Pt(L)₂]Cl₂, and [Au(L)₂]Cl, respectively. Infrared data revealed that the amlodipine besylate drug ligand chelated as monobasic tridentate through NH₂, oxygen (ether), and OH of besylate groups in Mn(II), Co(II), Ni(II), Zn(II), Cd(II), Mg(II), Sr(II), Ba(II), Ca(II), and Au(III) complexes, but in Pt(IV) and Pd(II) complexes, the amlodipine besylate coordinates via NH₂ and OH (besylate) groups. An octahedral geometry is proposed for all complexes except for the Cd(II), Pt(IV), and Pd(II) complexes. The amlodipine besylate free ligand and the transition and non-transition complexes showed antibacterial activity towards some Gram-positive and Gram-negative bacteria and the fungi (Aspergillus flavus and Candida albicans).     

Syntheses and electronic structures of one-electron-oxidized group 10 metal(II)-(disalicylidene)diamine complexes (metal = Ni, Pd, Pt)

Group 10 metal(II) complexes of H2tbu-salen (H2tbu-salen = N,N'-bis(3',5'-di-tert-butylsalicylidene)ethylenediamine) and H2tbu-salcn (H2tbu-salcn = N,N'-bis(3',5'-di-tert-butylsalicylidene)-1,2-cyclohexanediamine) containing two 2,4-di(tert-butyl)phenol moieties, [Ni(tbu-salen)] (1a), [Ni(tbu-salcn)] (1b), [Pd(tbu-salen)] (2a), [Pd(tbu-salcn)] (2b), and [Pt(tbu-salen)] (3), were prepared and structurally characterized by X-ray diffraction, and the electronic structures of their one-electron-oxidized species were established by spectroscopic and electrochemical methods. All the complexes have a mononuclear structure with two phenolate oxygens coordinated in a very similar square-planar geometry. These complexes exhibited similar absorption spectra in CH2Cl2, indicating that they all have a similar structure in solution. Cyclic voltammograms of the complexes showed a quasi-reversible redox wave at E1/2 = 0.82-1.05 V (vs Ag/AgCl), corresponding to formation of the relatively stable one-electron-oxidized species. The electrochemically oxidized or Ce(IV)-oxidized species of 1a, 2a, and 3 displayed a first-order decay with a half-life of 83, 20, and 148 min at -20 degrees C, respectively. Ni(II) complexes 1a and 1b were converted to the phenoxyl radicals upon one-electron oxidation in CH2Cl2 above -80 degrees C and to the Ni(III)-phenolate species below -120 degrees C. The temperature-dependent conversion was reversible with the Ni(III)-phenolate ground state and was found to be a valence tautomerism governed by the solvent. One-electron-oxidized 1b was isolated as [Ni(tbu-salcn)]NO3 (4) having the Ni(II)-phenoxyl radical ground state. One-electron-oxidized species of the Pd(II) complexes 2a and 2b were different from those of the Ni(II) complexes, the Pd(II)-phenoxyl radical species being the ground state in CH2Cl2 in the range 5-300 K. The one-electron-oxidized form of 2b, [Pd(tbu-salcn)]NO3 (5), which was isolated as a dark green powder, was found to be a Pd(II)-phenoxyl radical complex. On the other hand, the ESR spectrum of the one-electron-oxidized species of Pt(II) complex 3 exhibited a temperature-independent large g anisotropy in CH2Cl2 below -80 degrees C, while its resonance Raman spectrum at -60 degrees C displayed nu8a of the phenoxyl radical band at 1600 cm-1. These results indicated that the ground state of the Pt(II)-phenoxyl radical species has a large distribution of the radical electron spin at the Pt center. One-electron oxidation of 3 gave [Pt(tbu-salen)]NO3 (6) as a solid, where the oxidation state of the Pt center was determined to be ca. +2.5 from the XPS and XANES measurements.     

Vinyl-vinyl coupling on late transition metals through C-C reductive elimination mechanism. A computational study

A detailed density functional study was performed for the vinyl-vinyl reductive elimination reaction from bis-sigma-vinyl complexes [M(CH=CH(2))(2)X(n)]. It was shown that the activity of these complexes decreases in the following order: Pd(IV), Pd(II) > Pt(IV), Pt(II), Rh(III) > Ir(III), Ru(II), Os(II). The effects of different ligands X were studied for both platinum and palladium complexes, which showed that activation barriers for C-C bond formation reaction decrease in the following order: X = Cl > Br, NH(3) > I > PH(3). Steric effects induced either by the ligands X or by substituents on the vinyl group were also examined. In addition, the major factors responsible for stereoselectivity control on the final product formation stage and possible involvement of asymmetric coupling pathways are reported. In all cases DeltaE, DeltaH, DeltaG, and DeltaG(aq) energy surfaces were calculated and analyzed. The solvent effect calculation shows that in a polar medium halogen complexes may undergo a reductive elimination reaction almost as easily as compounds with phosphine ligands.     

Acetothioacetanilide as a gravimetric reagent for palladium, platinum and rhodium

Acetothioacetanilide, CH(3)CO . CH(2) . CS . NH . C(6)H(5) is found to be a very suitable gravimetric reagent for Pd(II), Pt(II) and Rh(III). The complexes [composition, M(C(10)H(10)NOS)(2); for M = Pd(II) and Pt(II), and M(C(10)H(10)NOS)(3)] are stable and can be weighed after drying at 105-110 degrees . Separation from base metals has been studied, and a structural interpretation made from DTA, TG and infrared data.     

Structures and optical and electrochemical properties of the Pt(II) and Pd(II) complexes with cyclometallated 2-phenylbenzothiazole and 1,4,7-trithiocyclononane

The distorted square pyramidal structures of the Pt(II) and Pd(II) complexes with cyclometallated 2-phenylbenzothiazole and flexible 1,4,7-trithiocyclononane are shown by X-ray diffraction analysis, IR spectroscopy, and ¹Н, ¹³С{¹H{, and ¹⁹⁵Pt NMR spectroscopy. The axial interaction of the d _Z2 orbital of Pt(II) and Pd(II) with the S atom of 1,4,7-trithiocyclononane results in the temperature quenching of the intraligand phosphorescence of the cyclometallated complexes in a solution and the one-electron ligand- and metal-centered reduction and oxidation of the complexes with the formation of the relatively stable Pd(III) complex (CIF file CCDC no. 1483011).     

Synthesis of N-Methyl-2-Thioimidazole Resin and Its Complex Behavior for Noble Metal Ions

The functional group capacity and the percentage of functional group conversion of crosslinked polystyrene resin bearing N-methyl-2-thioimidazole (MTIR) synthesized under optimum conditions are as high as 4.08 mmol/g resin and 96.0%, respectively. The apparent activation energies of sorption of MTIR for Au(III) and Pt(IV) are 13.1 and 13.4 kJ/mol, respectively. The sorption behavior of MTIR for Au(III), Pt(IV), and Pd(II) obeys the Freundlich and Langmuir isotherms. The sorption capacities of MTIR for Au(III), Pt(IV), and Pd(II) are as high as 4.33, 2.12, and 2.33 mmol/g resin, respectively. Au(III), Pt(IV), and Pd(II) adsorbed on MTIR can be eluted quantitatively by the eluant. The resin can be regenerated easily and reused without an obvious decrease in the sorption capacity for Au(III) and Pd(II). The resin has high sorption selectivity for noble metal ions. Au(III) can be separated quantitatively in the presence of high concentrations of Cu²⁺, Fe³⁺, Ni²⁺, and Mn²⁺. The recovery of platinum from the spent industrial catalysts is 98.6% by MTIR. The preconcentration and separation of palladium and platinum from the anode deposits of electrolysis of crude copper have been investigated. The resin may have potential industrial uses.     

Symmetrical and unsymmetrical pincer complexes with group 10 metals: synthesis via aryl C-H activation and some catalytic applications

Aryl-based pincer metal complexes with anionic terdentate ligands have been widely applied in organic synthesis, organometallic catalysis and other related areas. Synthetically, the most simple and convenient method for the construction of these complexes is the direct metal-induced C(aryl)-H bond activation, which can be fulfilled by choosing the appropriate functional donor groups in the two side arms of the aryl-based pincer preligands. In this perspective, we wish to summarize some results achieved by our group in this context. Successful examples include symmetrical chiral bis(imidazoline) NCN pincer complexes with Ni(II), Pd(II) and Pt(II), bis(phosphinite) and bis(phosphoramidite) PCP pincer Pd(II) complexes, unsymmetrical (pyrazolyl)phosphinite, (amino)phosphinite and (imino)phosphinite PCN pincer Pd(II) complexes, chiral (imidazolinyl)phosphinite and (imidazolinyl)phosphoramidite PCN pincer complexes with Ni(II) and Pd(II) as well as unsymmetrical (oxazolinyl)amine and (oxazolinyl)pyrazole NCN' pincer Pd(II) complexes. Among them, the P-donor containing complexes are efficiently synthesized by the "one-pot phosphorylation/metalation" method. The obtained symmetrical and unsymmetrical pincer complexes have been used as catalysts in Suzuki-Miyaura reaction (Pd), asymmetric Friedel-Crafts alkylation of indole with trans-β-nitrostyrene (Pt) as well as in asymmetric allylation of aldehyde and sulfonimine (Pd). In the Suzuki couplings conducted at 40-50 °C, some unsymmetrical Pd complexes exhibit much higher activity than the related symmetrical ones which can be attributed to their faster release of active Pd(0) species resulting from the hemilabile coordination of the ligands. Literature results on the synthesis of some related pincer complexes as well as their activities in the above catalytic reactions are also presented.     

Distribution coefficients and cation-exchange behaviour of some ammines and aquo complexes of metallic elements in ammonium nitrate solution

Comparative cation-exchange distribution coefficients of ammines and aquo complexes of Cu(II), Ni(II), Cd, Zn, Ag, Co(II)/(III), Hg(II), Pd(II), Au(III) and Pt(II) were determined in 0.1, 0.2, 0.5 and 1.0 M ammonium nitrate solution. The values for mercury(II) in ammonium chloride and of the ammine of copper(II) in ammonium citrate and ammonium sulphosalicylate solutions were also measured. The ion-exchange behaviour of the ammines is discussed and some possible separations are demonstrated by the experimental elution curves for the ion pairs Mg-Ni(II), Ca-Zn, Yb-Cd and Fe(III)-Cu(II).