Substoichiometric determination of traces of palladium by neutron-activation analysis

A highly selective, rapid one-step radiochemical separation procedure for palladium has been developed. It is based on the solvent extraction of palladium diethyldithiocarbamate from a 5M hydrochloric acid solution with a substoichiometric amount of copper diethyldithiocarbamate in chloroform. The separation has been applied to the determination of traces of palladium by neutron-activation analysis, in platinum, the rocks W-1 and PCC-1 and a biological material (kale). Amounts of palladium down to 10(-8) g have been determined.     

Substoichiometric extraction of gold(III). Determination of the extraction constant of gold dichloride diethyldithiocarbamate

The extraction constant of gold dichloride diethyldithiocarbamate has been determined (log K = 68.2 ± 0.2) by studying the competition from palladium in the substoichiometric extraction of gold with copper diethyldithiocarbamate in chloroform. Experimental conditions that allowed the equilibrium to be reached for any palladium concentration were chosen so that the influence of the palladium concentration on the extraction kinetics has also been studied. A program for the computation of any stability constant from extraction data for mixtures of three cations has been written.     

Thermodynamic stability and acidic properties of platinum(II) and palladium(II) bromide complexes

The instability constants of the platinum(II) and palladium(II) bromide complexes have been determined by potentiometry. The thermodynamic stability has been found to depend on the geometric structure of the complex and the nature of the central atom. The acid dissociation constants of the aqua complexes have been determined from pH measurements of the equilibrated solutions.     

Structure determination of a key intermediate of the enantioselective Pd complex catalyzed allylic substitution reaction

The structure of a catalytic intermediate with important implications for the interpretation of the stereochemical outcome of the palladium complex catalyzed allylic substitution with phosphino-oxazoline (PHOX) ligands is determined by liquid state NMR. The complex displays a novel structure that is highly distorted compared with other palladium eta2-olefin complexes known so far. The structure has been determined from nuclear overhauser data (NOE), scalar coupling constants, and long range projection angle restraints derived from dipole dipole cross-correlated relaxation of multiple quantum coherence. The latter restraints have been implemented into a distance geometry protocol. The projection angle restraints yield a higher precision in the determination of the relative orientation of the two molecular moieties and are essential to provide an exact structural definition of the olefinic part of the catalytic intermediate with respect to the ligand.     

Heteroleptic dipyrrinato complexes containing 5-ferrocenyldipyrromethene and dithiocarbamates as coligands: selective chromogenic and redox probes

Six heteroleptic dipyrrinato complexes [Ni(fcdpm)(dedtc)] (1), [Ni(fcdpm)(dipdtc)] (2), [Ni(fcdpm)(dbdtc)] (3), [Pd(fcdpm)(dedtc)] (4), [Pd(fcdpm)(dipdtc)] (5), and [Pd(fcdpm)(dbdtc)] (6) (fcdpm = 5-ferrocenyldipyrromethene; dedtc = diethyldithiocarbamate; dipdtc = diisopropyldithiocarbamate; dbdtc = dibutyldithiocarbamate) have been synthesized and characterized by elemental analyses and spectral (ESI-MS, IR, (1)H, (13)C NMR, UV-vis) and electrochemical studies. Crystal structures of 1, 2, 4, and 5 have been authenticated by X-ray single-crystal analyses. Nickel-based complexes 1-3 display selective chromogenic and redox sensing for Hg(2+) and Pb(2+) ions, while palladium complexes 4-6 display selective chromogenic and redox sensing only for Hg(2+). Electronic absorption, ESI-MS, and electrochemical studies indicated that sensing arises from interaction between 1-3 and Hg(2+)/Pb(2+) through sulfur of the coordinated dithiocarbamates, while it arises from the pyrrolic nitrogen of fcdpm and dithiocarbamate sulfur from 4-6 and Hg(2+). Different modes of binding between Ni and Pd complexes have further been supported by theoretical studies. The receptor-cation binding constants (K(a)) and stoichiometry between probes and Hg(2+)/Pb(2+) have been estimated by the Benesi-Hildebrand method and Job's plot analysis. Detection limits for 1-3 toward Hg(2+)/Pb(2+) and 4-6 for Hg(2+) have been found to be reasonably high.     

Ternary complexes of palladium(II) and selected amines

Summary The formation and equilibria of the binary and ternary palladium(II) complexes of diethylenetriamine (dien) with other selected amines have been investigated. The results of pH titration measurements allowed the calculation of equilibrium constants, characteristic for the binary and ternary complexes formed. The concentration distribution of various complex species was evaluated and the chelation mode ascertained by conductivity measurements.     

Synthesis, characterization and cation-induced dimerization of new aza-crown ether-appended metalloporphyrins

New metalloporphyrins bearing one or two aryl-aza-crown ether moieties at meso-positions have been synthesized using a palladium catalyzed amination reaction and fully characterized by spectral techniques. X-Ray structural data have been presented for the zinc and copper complexes of mono-substituted aza-crown ether appended metalloporphyrins. UV-Vis and (1)H NMR spectroscopic studies showed that addition of K(+) cations to a solution of monomeric aza-crowned porphyrins in CHCl(3)/MeOH led to cation-induced dimerization of these porphyrins, whereas addition of Na(+) cations yielded a monomeric complex. Axial coordination of the exobidentate ligand (DABCO) to zinc complexes of aza-crowned porphyrins and following binding metal ions led to formation of sandwich complexes with high stability constants.     

Interaction of palladium with sulphaguanidine

The formation constants of palladium with chloride ions have been determined by a new approach to the interpretation of the ultraviolet spectra. The interaction of PdCl(4)(2-) with sulphaguanidine (SG) has been interpreted and evaluated quantitatively. The formation constants of the mixed ligand complex Pd(SG)(2),Cl(2), were determined spectrophotometrically. The stability constants for the stepwise formation of the palladium chloride complexes are: log k(1) = 3.48; log k(2) = 2.79; log k(3) = 2.35; log k(4) = 1.1, and for the interaction of PdCl(4)(2-) with SG, log k(1) = 5.42; log k(2) = 4.38.     

Kinetics of electrochemical reduction of 2-carbomethoxy-1,1-dichloro-2-methylcyclopropane by the double mediator system anthracene-PtII,PdII, and NiII complexes of cyclic aminomethylphosphines

Effective rate constants of homogeneous reduction of 2-carbomethoxy-1,1-dichloro-2-methylcyclopropane have been calculated by the polarographic method of determining the catalytic increase in the limiting current of the reduction wave of mediators,i.e., individual complexes of platinum, palladium or nickel with cyclic aminomethylphosphines and their combination with anthracene radical anions. Platinum compounds show higher catalytic activity than palladium and nickel complexes in direct reduction with metallocomplexes. The catalytic activity of a double mediator system for the majority of metallocomplexes is higher than the total catalytic activity of the individual metallocomplex and organic carrier.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No.3, pp. 414–416, March, 1994.The authors are grateful to G. N. Nikonov for the aminomethylphosphine complexes.     

Spectrophotometric study of the complex formation of 3-(1-naphthyl)-2-mercaptopropenoic acid with nickel(II), palladium(II) and hydrogen ions

The equilibria between 3-(1-naphthyl)-2-mercaptopropenoic acid (H(2)NMP) and nickel, palladium and hydrogen ions at 25 degrees in aqueous 0.1 M NaClO(4) solution containing 1-2% ethanol have been studied spectrophotometrically. Protonation constants for the ligand and formation constants for the complexes Ni(NMP), Ni(NMP)(2-)(2), Pd(NMP) and Pd(NMP)(2-)(2), refined by the SQUAD program, are reported.     

Complexation reactions of pyridinols

Complexation of iron(III) with several pyridinols has been studied and used in selective detection and determination (spectrophotometric and chelatometric) of the metal. Iron(III)-pyridinol complexes are also used as indicators in acid-base titrations. A thiol group vicinal to a phenol group in a pyridine molecule provides a reagent that is a suitable ligand for palladium(II) determination. Stability constants of bivalent metal complexes with pyridinols have been determined potentiometrically.     

Orthopalladated and -platinated bulky triarylphosphite complexes: synthesis,reactivity and application as high-activity catalysts for Suzuki and Stille coupling reactions

Bulky triarylphosphite ligands undergo facile orthometallation reactions with palladium and platinum precursors. The crystal structure of an example of the resultant palladacycles has been determined. The reactivity of some of the metallacycles with HCl, monodentate and bidentate phosphines and sodium diethyldithiocarbamate has been investigated, and the crystal structure of a diethyldithiocarbamate adduct of a palladacycle is presented. The palladacyclic complexes prove to be extremely active catalysts for the Suzuki coupling of aryl bromides with aryl boronic acids. They can also be used as catalysts for the coupling of alkylboronic acids. Meanwhile di- and trialkyl phosphine adducts of one of the palladacycles shows very high activity in the Suzuki coupling of aryl chlorides and can also be used to good effect for the Stille coupling of these substrates. The role of the phosphite ligand in the Suzuki coupling of aryl chlorides seems to be one of increasing catalyst longevity by stabilisation of the Pd(0) resting state.     

“Through-space” P spin-spin couplings in ferrocenyl tetraphosphine coordination complexes: Improvement in the determination of the distance dependence of JPP constants

From the analysis of several nickel and palladium halide complexes of a constrained ferrocenyl tetraphosphine, the existence in solution phase of unique ³¹P-³¹P “through-space” nuclear spin-spin coupling constants (J_PP) had been previously evidenced. Due to the blocked conformation of the species in solution, and based on the NMR spectra obtained for the complexes and their corresponding solid state X-ray structures, these J_PP constants had been shown to clearly depend on the mutual spatial position of the corresponding phosphorus atoms. Herein, the quantitative correlation disclosed at that time (P?P distance dependence of coupling constants) is remarkably confirmed, and mathematically refined owing to the study of a new palladium dibromide tetraphosphine complex, for which the synthesis and the solution NMR and solid state X-ray characterizations are reported.     

Synthesis, luminescence and ion-binding properties of palladium(II) complexes with 1,2-bis[di(benzo-15-crown-5)phosphino]ethane (dbcpe)

A series of palladium(II) complexes with 1,2-bis[di(benzo-15-crown-5)phosphino]ethane ligand (dbcpe), [Pd(dbcpe)X2] (X = Cl 1, Br 2 and I 3), have been successfully synthesised and characterised. The X-ray crystal structure of dbcpe has also been determined. The cation-binding properties of the complexes have been studied and the stability constants with alkali metal cations determined. The crown-free analogue of dbcpe, 1,2-bis[bis(3,4-dimethoxyphenyl)phosphino]ethane (ddmppe), and the related complexes have also been prepared and comparison studies have been made.     

Synthesis and structural characterization of binuclear palladium(II) complexes of salicylaldimine dithiosemicarbazones

A series of binuclear palladium(II) salicylaldiminato dithiosemicarbazone complexes have been synthesized and characterized. The palladium complexes were obtained by the reaction of various ethylene- and phenylene-bridged dithiosemicarbazones with Pd(PPh₃)₂Cl₂. The free salicylaldimine ligands and their palladium complexes were characterized by NMR and IR spectroscopies, ESI-mass spectrometry, elemental analyses and for two representative complexes also by X-ray diffraction. In both metal complexes, the solid-state structures show the two palladium centers to be coordinated in a slightly distorted square-planar geometry, which gives rise in each case to five- and six-membered chelate rings. The salicylaldimine thiosemicarbazone ligands coordinate to palladium in a tridentate manner, through the phenolic oxygen, imine nitrogen and thiolate sulfur atoms.     

Reaction of platinum (II) and palladium (II) nitrite complexes with potassium bromide

The reaction of nitrite-bridged binuclear platinum and palladium complexes and KBr in aqueous solution is studied. It is shown that the Pt-O-N bridging bond dissociates during the reaction to yield two mononuclear complexes. Rate constants of the reaction at 15°C are determined.     

Vibrational circular dichroism spectroscopy of two chiral binaphthyl diphosphine ligands and their palladium complexes in solution

BINAP (2,2'-diphenylphosphino-1,1'-binaphthyl) is a unique binaphthyl diphosphine ligand with axial chirality. The palladium complexes of BINAP and of its derivative TOLBINAP have found extensive applications in the field of asymmetric syntheses. The conformational changes in the BINAP and TOLBINAP ligands before and after coordination with palladium have been investigated using density functional theory, vibrational absorbance (VA) and vibrational circular dichroism (VCD) spectroscopy. VA and VCD spectra of these two chiral ligands and their corresponding palladium complexes have been recorded in CDCl(3) solution. Extensive conformational searches have been carried out for both the ligands and the associated palladium complexes. Coordination with palladium has been found to introduce structural rigidity to the ligands. The calculated VA and VCD spectra of the ligands and complexes in the gas phase show substantial differences to the experimental data. Incorporation of the implicit polarisable continuum solvation model has provided much better agreement between theory and experiment, especially for the complexes, allowing clear identification of the species and conformations. This and the high specificity of VCD spectral signatures to chirality and to conformations suggest the potential applications of VCD spectroscopy for following these important catalytic species in solution reactions directly.     

Determination of the extraction constant of gold diethyldithiocarbamate dichloride by substoichiometric extraction

Radioactive gold(III) with radioactive palladium(II) as reference ion in a chloride medium was substoichiometrically extracted with zinc diethyldithiocarbamate in chloroform. A formula for calculation of the extraction constant of the gold(III) complex was derived, for which only the values of distribution ratios of gold and palladium between the two phases had to be measured experimentally. The extraction constant was found to be log K = 68.9 ± 0.4.     

ESR, electrochemical and reactivity studies of antitrypanosomal palladium thiosemicarbazone complexes

Cyclic voltammetry (CV) and electron spin resonance (ESR) techniques were used in the investigation of novel palladium complexes with bioactive thiosemicarbazones derived from 5-nitrofurane or 5-nitrofurylacroleine. Sixteen palladium complexes grouped in two series of the formula [PdCl(2)HL] or [PdL(2)] were studied. ESR spectra of the free radicals obtained by electrolytic reduction were characterized and analyzed. The ESR spectra showed two different hyperfine patterns. The stoichiometry of the complexes does not seem to affect significantly the hyperfine constants however we observed great differences between 5-nitrofurane and 5-nitrofurylacroleine derivatives. The scavenger properties of this family of compounds were lower than Trolox.     

Gold and palladium: their diethyldithiocarbamate complexes. composition,structure and analysis

A study was made of the composition and behaviour of complexes formed at different pH's between gold(III) and palladium(II) with sodium diethyldithiocarbamate. The complexes obtained are: Pd(CBM)₂ (insoluble); [Au(CBM)]⁺² (insoluble); [Au₂(CBM)₃)⁺³ (soluble); [Au(CBM)₂]⁺ (soluble).Analytical methods are presented for the determination of gold and palladium in mixtures. The heterometric curves obtained permit the determination of gold as well as of palladium in a single titration, with an error of 0–2%.