Luminescent, three-coordinate azadipyrromethene complexes of d(10) copper, silver, and gold

Boron azadipyrromethenes are red-light-absorbing dyes with chromophoric capabilities deriving from a conjugated, chelating framework. Reported here are tricoordinate copper(I), silver(I), and gold(I) complexes of a tetraphenylazadipyrromethene ligand. The new complexes are characterized by optical absorption and emission spectroscopy, multinuclear NMR, mass spectrometry, elemental analysis, and X-ray diffraction crystallography. Time-dependent density functional theory calculations indicate that the principal absorption features in azadipyrromethene complexes result from optically allowed intraligand transitions that undergo configuration interaction.     

Theoretical investigation on DNA/RNA base pairs mediated by copper, silver, and gold cations

B3LYP density functional based computations were performed in order to characterize the interactions present in some Cu(+), Ag(+), and Au(+) metal ion-mediated DNA and RNA base pairs from both structural and electronic points of view. Examined systems involve as ligands canonical Watson-Crick, Hoogsteen and Wobble base pairs. Two artificial Hoogsteen base pairs were also taken into account. Binding energy values indicate that complexes involving silver cations are less stable than those in which copper or gold are present, and propose a similar behaviour for these two latter ions. The nature of the bond linking metal ions and bases was described by the NBO analysis that suggests metal coordinative interactions to be covalent. An evaluation of the dispersion contributions for the investigated systems was performed with the B3LYP-D3 functional.     

Superconductivity in copper, silver, and gold compounds

High-temperature superconductivity exists in layered, square-planar cuprates, but is almost absent in most other Cu(II) compounds and in most Ag(II) and Au(II) compounds. Valence state II is quite unusual in silver and gold and often disproportionates to valence states I and III ("negative-U compounds"). The two-electron difference in oxidation state is suggestive of electron pairing, a prerequisite for superconductivity. In the present paper the connection between disproportionation and geometrical structure on one hand and superconductivity on the other is discussed by using the accepted theory for mixed valence complexes. It is concluded that absence of superconductivity in gold and silver compounds can be connected to the instability of oxidation state II and the large difference in equilibrium geometry between oxidation states I and III.     

Complexes of copper and silver with tetracyanobiimidazole

We have recently reported the synthesis and properties of a remarkable new ligand 4,4′,5,5′-tetracyano-2,2′-biimidazole (H₂Tcbiim).¹ This acidic ligand readily binds metal ions in its dianionic form and appears to act as a strong pi acceptor. Its use as a quadridentáte bridging ligand allows study of metal-metal interactions through a planar conjugated system and extends earlier work by us² and by Hendrickson and coworkers³ on 2,2′-biimidazole. In this communication we report on the reactions of H₂Tcbiim with Ag(I), Cu(I) and Cu(II) salts.     

Thermodynamics of copper,silver, gold,and mercury acetylenides

Thermodynamic characteristics of the copper, silver, gold, and mercury acetylenides obtained from the data of precise calorimetric measurements in the region from 5 to 340 K are considered. Tables of the thermodynamic functions C _p°(T), H°(T) — H°(0), S°(T), and G°(T) — H°(0) at 0—340 K, standard enthalpies of combustion H _c°, and thermodynamic characteristics of formation of the acetylenides from simple substances H _f°, S _f°, G _f°, and logK _f° at 298.15 K and standard pressure are presented. Temperature plots of the heat capacity of the acetylenides were analyzed in the framework of Tarasov's theory and the fractal version of Debye's theory of heat capacity. The values of heat capacity of several acetylenides yet unstudied were estimated.     

Fire-assay collection of gold and silver by copper

Gold and silver are very effectively collected in copper after fire-assay fusion at 1200 degrees . The resultant copper button is dissolved in perchloric acid and the parting solution is diluted with an equal volume of water. Both gold and silver are precipitated in the copper perchlorate medium by reduction with formic acid or hydroquinone. The two noble metals are collected, dissolved in acids, and determined by atomic-absorption spectrometry. The proposed procedure is simple, relatively rapid, and has been successfully applied to ores, concentrates, furnace products, and copper alloys. Recoveries compare favourably with those obtained by the classical lead cupellation method.     

Biamperometric determination of copper,silver and gold with ascorbic acid

The simultaneous determination of milligram amounts of copper, silver and gold in mixtures is described. Ascorbic acid is added in excess and back-titrated biamperometrically with standard potassium iodate solution. Mixtures can be analyzed by using precipitation and masking     

Hydrated copper and gold monovalent cations: Ab initio study

To understand the hydration phenomena of noble transition metals, we investigated the structures, hydration energies, electronic properties, and spectra of the Cu(+)(H(3)O)(1-6) and Au(+)(H(2)O)(1-6) clusters using ab initio calculations. The coordination numbers of these clusters are found to be only two, which is highly contrasted to those of Ag(+)(H(2)O)(n) (which have the coordination numbers of 3-4) as well as the hydrated alkali metal ions (which have the coordination numbers of approximately 6). For the possible identification of their interesting hydration structures, we predict their IR spectra for the OH stretch modes.     

Complexes of some bivalent cobalt,nickel, copper,zinc, cadmium and monovalent silver salts with 4,4′-BipyridylN,N′-dioxide

Summary Coordination compounds have been prepared from 4,4-hipyridylN,N-dioxide (4,4-BipyO₂) and some hivalent metal halides, nitrates and thiocyanates as well as silver(1) nitrate.viz., Co(4.4-BipyO₂)₂Cl₂, Co(4.4-BipyO₂)Br₂, Co(4,4-Bi-pyO₂)(NO₃)₂. Co(4,4-BipyO₂)₂(NCS)₂. Ni(4.4-BipyO₂)₂Cl₂. Ni(4,4-BipyO₂)(NO₃)₂, Ni₂(4.4-BipyO₂)₃(NSC)₄. Cu(4,4-BipyO₂)(NO₃)₂. Zn(4,4-BipyO₂(NO₃)₂, Zn,(4.4-BipyO₂)₃-(NCS)₄. Cd(4.4-BipyO₂)(NO₃)₂, Cd(4.4-BipyO₂)₂(NCS)₂ and Ag(4,4-BipyO₂)(NO₃). The products were characterized by magnetic susceptibility. electronic and i.r. spectral measurements down to 200 cm^–1. Tentative stereochemistries for the complexes isolated in the solid state are proposed. The ligand field parameters 111 Dy. B. j3. )., and calculated for the cobalt. nickel and copper complexes are consistent with these stereochemistries.     

Donnan dialysis of copper, gold and silver cyanides with various anion exchange membranes

Donnan dialysis is an ion exchange membrane process that can be used for the purification and concentration of diluted solutions. In this work, the behaviour of gold, silver and copper in cyanide medium is examined. Flux of cyanide complexes and corresponding free cyanide are determined using five commercial anion exchanger membranes (AMV, ACS, RAI 5035, ADP and ADS). The results show that the rate transfer depends upon the nature of the anion exchanger membrane. It is observed that the species number in the feed solution influences the transfer selectivity of metal ion complex against free cyanide Thus, gold which forms only one stable species with cyanides is transferred faster through an ACS membrane than copper which forms three species. However, this result is not verified when an ADS membrane is used. A model of the complex transfer through anion exchange membranes based on Donnan dialysis is proposed. A three compartment Donnan dialysis is performed to improve the separation between the studied metals. Decyanidation is also examined and separation factors are calculated. It is shown that Donnan dialysis can be an efficient technique for the separation of cyanides complexes of copper, gold and silver when parameters such as anion exchange membrane and the number of compartments are optimised. An advantage of this technique is also the possibility of recycling all reactants with a good impact on the environment.     

Adsorption mechanisms of sulfathiazole on gold,silver and copper surfaces studied by SERS

Surface-enhanced Raman scattering (SERS) of sulfathiazole was studied in gold, silver and copper colloids as well as on a gold plate. SERS spectra of sulfathiazole in gold and silver colloids indicated chemisorption of molecules on the metal nanoparticles through the amide nitrogen, with the phenyl moiety orthogonally placed and the thiazole ring almost parallel positioned towards the metal surface. Although selectively enhanced phenyl bands pointed to a very similar position of the sulfathiazole molecules on the copper colloid, a chemical bonding was not implied. Unlike adsorption mechanisms and position of the molecules on the colloid metal surfaces, a sideway adsorption of sulfathiazole on the gold plate was proposed. Hereby, both, the amide nitrogen and the thiazole nitrogen were considered responsible for approaching of sulfathiazole to the gold enhancing surface.     

Nonlinear d10-ML2 Transition-Metal Complexes

Invited for this month′s cover is the group of Prof. F. Matthias Bickelhaupt. The cover picture illustrates the authors′ quantum chemical finding that π electrons can significantly bend otherwise linear d¹⁰-ML₂ complexes through backbonding. For more details, see the Full Paper on p. 106 ff.The Group of F. Matthias BickelhauptDepartment of Theoretical Chemistry Amsterdam Center for Multiscale Modeling VU University E-mail: ln.uv@tpuahlekciB.M.FInstitute for Molecules and Materials Radboud University Nijmegen     

Flame atomic absorption spectrometry of silver and gold in copper intermediates

The effect of hydrochloric acid and salts from the sample on the solubility of methyl isobutyl ketone (MIBK) in aqueous phase and the effect of hydrochloric acid concentration on the MIBK extraction of iron(III) and gold(III) were studied. As a result, an improved method by flame atomic absorption sepctrometry for determination of silver and gold in copper intermediates was developed, employing a more efficient removal of iron and special standards depending upon the concentration of salts introduced by different samples.     

Complexes of gold(I), silver(I), and copper(I) with pentaaryl[60]fullerides

Gold(I), silver(I), and copper(I) phosphine complexes of 6,9,12,15,18-pentaaryl[60]fullerides 1a and 1b, namely, [(4-MeC(6)H(4))(5)C(60)]Au(PPh(3)) (2a), [(4-t-BuC(6)H(4))(5)C(60)]Au(PPh(3)) (2b), [(4-MeC(6)H(4))(5)C(60)]Ag(PCy(3)) (3a), [(4-t-BuC(6)H(4))(5)C(60)]Ag(PPh(3)) (3b), [(4-t-BuC(6)H(4))(5)C(60)]Ag(PCy(3)) (3c), [(4-MeC(6)H(4))(5)C(60)]Cu(PPh(3)) (4a), and [(4-t-BuC(6)H(4))(5)C(60)]Cu(PPh(3)) (4b), have been synthesized and characterized spectroscopically. All complexes except for 3c were also characterized by single-crystal X-ray diffraction. Several coordination modes between the cyclopentadienyl ring embedded in the fullerene and the metal centers are observed, ranging from η(1) with a slight distortion toward η(3) in the case of gold(I), to η(2)/η(3) for silver(I), and η(5) for copper(I). Silver complexes 3a and 3b are rare examples of crystallographically characterized Ag(I) cyclopentadienyls whose preparation was possible thanks to the steric shielding provided by fullerides 1a and 1b, which stabilizes these complexes. Silver complexes 3a and 3b both display unexpected coordination of the cyclopentadienyl portion of the fulleride anion with Ag(I). DFT calculations on the model systems (H(5)C(60))M(PH(3)) and CpMPH(3) (M = Au, Ag, or Cu) were carried out to probe the geometries and electronic structures of these metal complexes.     

Determination of gold in silver, copper, lead, selenium and anode slime by atomic-absorption spectrometry

A simple and sensitive combined solvent-extraction and atomic-absorption spectrometric method has been developed for the determination of gold in silver, copper, lead, selenium and anode slime. Samples are decomposed with hydrochloric and nitric acids, and gold is extracted as the trioctylmethylammonium-gold bromide complex and determined by atomic-absorption spectrometry by direct spraying of the extract into the flame. Optimal conditions for the extraction and determination of gold have been established. As little as 0.5 mug of gold in a sample can be determined. The extraction of gold from hydrochloric or hydrobromic acid solution with trioctylamine or trioctylmethylammonium chloride (or bromide) has also been investigated.     

Optical spectra of protected diamine 10-bond-bridged intervalence radical cations related to N,N,N'N'-tetraalkylbenzidine

The optical absorption spectra of the delocalized intervalence radical cations of seven o,o'-linked benzidine derivatives that have the nitrogens protected as 9-(9-aza-bicyclo[3.3.1]nonan-3-one) derivatives are discussed and compared with that of the p-phenylene radical cation. The linking units are CH2, CH2CH2, NMe, S, SO2, and C=O, and we also studied H,H (the unlinked benzidine). The lowest-energy absorption band is assigned as the transition from the antibonding combination of symmetrical N and aromatic orbitals to the antibonding combination of the antisymmetric N and aromatic orbitals using TD-DFT calculations, and a good correlation between the observed transition energies and those calculated using the simple Koopmans theorem-based "neutral in-cation geometry" calculations on the UB3LYP/6-31G* structures is found. The use of the two-state model that equates the electronic interaction through the bridge between the amino groups with half of the lowest transition energy is seriously incorrect for these and other delocalized intervalence compounds. The problem of extracting the electronic interactions that actually are involved from calculated transition energies is discussed.     

The simultaneous determination of gold and silver in blister copper and speiss products

A method for determination of silver and gold (concentration ranges of 0.1–0.4% and 8·10^–4–3·10^–3% respectively) in blister copper and speiss is described. Silver is determined directly in the solution after dissolution of the sample and appropriate dilution. The amount of gold is determined in an aliquot of the same solution after extraction with methyl isobutyl ketone. The relative standard deviation of the method described is 3.3% for speiss and 4.4% for blister copper for gold and 1.6% and 2.5% for silver respectively.     

A study of aldehyde oxidation at glassy carbon,mercury, copper,silver, gold and nickel anodes

The rate, potential and mechanism of the anodic oxidation of aliphatic aldehydes have been found to be highly dependent on solution conditions and electrode material. Aldehyde oxidations in neutral acetonitrile on glassy carbon occur at very positive potentials (ca. +3 V vs. SCE) and the peak potentials correlate with the ionization potentials of the aldehydes. In aqueous base, aldehyde oxidation is assisted by reversible addition of hydroxide to the carbonyl group to form electroactive gem-diolate (II). Oxidations of aldehydes in aqueous base on Hg, Ni, Ag and Au all yield the corresponding carboxylate via two-electron oxidation plus aldol and Cannizzaro byproducts and the oxidations occur at potentials far negative of the unassisted oxidation in neutral acetonitrile. On Ni, Cu and possibly Hg the oxidation involves the formation of a metal oxide which acts as a chemical oxidizing agent. On Ag and Au the oxidations take place on a surface which is not covered by a phase oxide. A mechanism involving a direct electrochemical process with oxidation of gem-diolate adsorbed on an oxide-free metal surface is proposed. A pulsed electrolysis technique was utilized to circumvent deactivation of Ag and Au electrodes during electrolysis and preparation of an “aurized” gold surface with a much slower deactivation rate is described.