Protonation equilibria and solubility of l-cystine

l-Cystine is the natural least soluble of the naturally occurring amino acids. Its solubility is a function of the hydrogen ion concentration depending on its protonation. This paper presents an investigation on properties of l-cystine in a constant ionic medium of NaCl at different concentrations (3.00,2.00,1.00,0.500,0.150 mol dm(-3)) and at 25 degrees C. In such experimental conditions, solubility and its changes as a function of hydrogen ion concentration were determined. Protonation of cystine was studied in acid and basic solution, by measuring the electromotive force of galvanic cell involving a glass electrode. Four protonation constants for l-cystine were determined in all the selected concentrations of ionic medium. The different values obtained for the constants in ionic medium of different concentration could be explained both with the variation of activity coefficients or with the complex formation between l-cystine and sodium ions. Variations of solubility for different concentration of NaCl were observed as well.     

Thermal decomposition of some silver(I) carboxylates under nitrogen atmosphere

The thermal decomposition reactions of CH₃CH₂C(CH₃)₂COOAg (1), (CH₃)₃SiCH₂COOAg (2), CF₃COOAg (3), (CH₃)₃CCOOAg (4), C₂H₅COOAg (5), C₃F₇COOAg (6), C₆F₁₃COOAg (7) and (CF₂)₃(COOAg)₂ (8) were studied in N₂ atmosphere using thermogravimetry (TG), derivative thermogravimetry and differential thermal analysis. Characterized compounds decomposed in one- or multi-step processes with metallic silver formation in the range 215–465 °C. TG-IR studies of gases evolved during thermolysis revealed products of decomposition, such as carboxylic acids, CO₂ and recombination reactions.     

Toluene-sandwiched trinuclear copper(I) and silver(I) triazolates and phosphine adducts of dinuclear copper(I) and silver(I) triazolates

Cu (I) and Ag (I) complexes of the fluorinated triazolate ligand [3,5-(C3F7)2Tz](-) have been synthesized using the corresponding metal(I) oxides and the triazole. They form pi-acid/base adducts with toluene, leading to [Tol][M3][Tol] ([Tol]=toluene; [M3]={[3,5-(C3F7)2Tz]Cu}3 or {[3,5-(C3F7)2Tz]Ag}3) type structures. Packing diagrams show the presence of extended chains of the type {[Tol][M3][Tol]}infinity, but the intertoluene ring distances are too long for significant pi-arene/pi-arene contacts. These copper and silver triazolates react with PPh3 (at a 1:1 metal ion/P molar ratio), leading to dinuclear {[3,5-(C3F7)2Tz]Cu(PPh3)}2 and {[3,5-(C3F7) 2Tz]Ag(PPh3)}2. They feature a six-membered Cu(mu-N-N) 2Cu or Ag(mu-N-N)2Ag core with a boat conformation.     

Lyotropic mesomorphism in some thermotropic,polycatenar complexes of silver(I)

A wide range of mesophases are induced on treating polycatenar complexes of silver(I) with a wide range of organic solvents.     

A13C nuclear magnetic resonance study of some linear alkynyl gold(I) and silver(I) complexes

Summary Phenylacetylide gold(I) and silver(I) compounds of the type [n-Bu₄N][M(C=CPh)₂], (1) and [n-Bu₄N][XMC=CPh], (2) have been studied by¹³C n.m.r. spectroscopy and their chemical shifts are reported for the first time. The shielding of the alkynyl carbon linked directly to the metal in (2) isca. 10–15 ppm less than the analogous carbon in (1) (M=Au), andca. 6–11 ppm less in the silver complexes (M=Ag). The variation in chemical shift depends on the nature of X(X=Cl, Br, I, C₂Ph and Ph₃P) and indicates greatly different degrees of polarization of the Au-C= (or Ag-C=) bonds in (1) and (2). I.r. spectra of the title compounds are reported and confirm the weakness of ML back-bonding. Comparison is also made with¹³C and i.r. data for platinum, and mercury complexes.     

Dihydrogen Evolution by Protonation Reactions of Nickel(I)

Nickel-mediated formation of H(2) by protonation of Ni(I) has been established and the kinetics of the process investigated. The diamagnetic complex [Ni(II)(psnet)](BF(4))(2) was prepared and reduced to [Ni(I)(psnet)](BF(4)) with NaBH(4) in THF (psnet = bis(5-(diphenylphosphino)-3-thiapentanyl)amine). Both complexes were structurally characterized by X-ray diffraction. [Ni(psnet)](1+) was demonstrated to be an authentic Ni(I) complex with a.(d(z)()2)(1) ground state. Under appropriate conditions, [Ni(psnet)](+) reacts with acids in nonaqueous media to give near-quantitative yields of H(2) according to the stoichiometry Ni(I) + H(+) --> Ni(II) + (1)/(2)H(2). Dihydrogen production was demonstrated to be directly related to Ni(I) oxidation. The reaction system [Ni(psnet)](+)/HCl/DMF, which gives H(2) yields of greater, similar90%, was subjected to a kinetics analysis. The overall reaction [Ni(psnet)](+) + HCl --> [Ni(psnet)Cl](+) + (1)/(2)H(2) proceeds by two parallel pathways dependent on chloride concentration. Addition of Bu(4)NCl accelerates the reaction, whereas (Bu(4)N)(PF(6)) decreases the rate. A two-term rate law is presented which includes contributions from both pathways, whose common initial step is protonation of Ni(I). Path A (low chloride concentration) involves the formation and collapse of nickel hydride chloride ion pairs; the rate-determining step is the minimal reaction 2Ni(III)-H(-) --> H(2) + 2Ni(II). Path B (high chloride concentration) includes as the rate-limiting step collapse of a nickel hydride dichloride ion pair followed by the bimolecular reaction of two Ni(III)-H(-) intermediates or reduction to Ni(II)-H(-) by Ni(I) followed by protonation of the hydride. The relation of these results to the reactions of hydrogenase enzymes is considered.     

Protonation reactions of dinuclear pyrazolato iridium(I) complexes

The complex [[Ir(mu-Pz)(CNBu(t))(2)](2)] (1) undergoes double protonation reactions with HCl and with HO(2)CCF(3) to give the neutral dihydride complexes [[Ir(mu-Pz)(H)(X)(CNBu(t))(2)](2)] (X = Cl, eta(1)-O(2)CCF(3)), in which the hydride ligands were located trans to the X groups and in the boat of the complexes, both in the solid state and in solution. The complex [[Ir(mu-Pz)(H)(Cl)(CNBu(t))(2)](2)] evolves in solution to the cationic complex [[Ir(mu-Pz)(H)(CNBu(t))(2)](2)(mu-Cl)]Cl. Removal of the anionic chloride by reaction with methyltriflate allows the isolation of the triflate salt [[Ir(mu-Pz)(H)(CNBu(t))(2)](2)(mu-Cl)]OTf. This complex undergoes a metathesis reaction of hydride by chloride in CDCl(3) under exposure to the direct sunlight to give the complex [[Ir(mu-Pz)(Cl)(CNBu(t))(2)](2)(mu-Cl)]OTf. Protonation of both metal centers in [[Ir(mu-Pz)(CO)(2)](2)] with HCl occurs at low temperature, but eventually the mononuclear compound [IrCl(HPz)(CO)(2)] is isolated. The related complex [[Ir(mu-Pz)(CO)(P[OPh](3))](2)] reacts with HCl and with HO(2)CCF(3) to give the neutral Ir(III)/Ir(III) complexes [[Ir(mu-Pz)(H)(X)(CO)(P[OPh](3))](2)], respectively. Both reactions were found to take place stepwise, allowing the isolation of the intermediate monohydrides. They are of different natures, i.e., the metal-metal-bonded Ir(II)/Ir(II) compound [(P[OPh](3))(CO)(Cl)Ir(mu-Pz)(2)Ir(H)(CO)(P[OPh](3))] and the mixed-valence Ir(I)/Ir(III) complex [(P[OPh](3))(CO)Ir(mu-Pz)(2)Ir(H)(eta(1)-O(2)CCF(3))(CO)(P[OPh](3))].     

Fluorescent detection of silver(I) and cysteine using SYBR Green I and a silver(I)-specific oligonucleotide

We report on a novel method for the determination of silver ion (Ag⁺) and cysteine (Cys) by using the probe SYBR Green I (SGI) and an Ag+-specific cytosine-rich oligonucleotide (C-DNA). The fluorescence of SGI is very weak in the absence or presence of randomly coiled C-DNA. If, however, C-DNA interacts with Ag⁺ through the formation of cytosine-Ag⁺-cytosine (C-Ag⁺-C) base pairs, the randomly coiled C-DNA undergoes a structural changes to form a hairpin-like structure, thereby increasing the fluorescence of SGI. This fluorescence turn-on process allows the detection of Ag⁺ in the 10–600?nM concentration range, with a detection limit of 4.3?nM. Upon the reaction of Ag⁺ with Cys, Cys specifically removes Ag⁺ from the C-Ag⁺-C base pairs and destroys the hairpin-like structure. This, in turn, results in a decrease in fluorescence intensity. This fluorescence turn-off process enables the determination of Cys in the 8–550?nM concentration range, with a detection limit of 4.5?nM. The method reported here for the determination of either Ag⁺ or Cys is simple, sensitive, and affordable, and may be applied to other detection systems if appropriately selected DNA sequences are available.

A calorimetric study of the silver (I) complexes of some sulfur-containing amines

The enthalpies of the reactions in 0.5 M KNO₃ at 25°C between the hydrogen and silver(I) ions and a number of sulfur-containing amines of the general formula R'-S-(CH₂)NR₂ where

and n=2,3, have been determined by means of direct calorimetric titrations. By the use of the ΔG values reported elsewhere, the corresponding ΔS values have been calculated. the complex formation in acid, neutral and alkaline medium is discussed.     

Photosensitive azobispyridine gold(I) and silver(I) complexes

The neutral and cationic dinuclear gold(I) compounds [(μ-N-N)(AuR)(2)] (N-N = 2,2'-azobispyridine (2-abpy), 4,4'-azobispyridine (4-abpy); R = C(6)F(5), C(6)F(4)OC(12)H(25)-p, C(6)F(4)OCH(2)C(6)H(4)OC(12)H(25)-p) and [(μ-N-N){Au(PR(3))}(2)](CF(3)SO(3))(2) (N-N = 2-abpy, 4-abpy, R = Ph, Me) have been obtained by displacement of a weakly coordinated ligand by an azobispyridine ligand. The corresponding silver(I) dinuclear [(μ-2-abpy){Ag(CF(3)SO(3))(PPh(3))}(2)] and polynuclear [{Ag(CF(3)SO(3))(4-abpy)}(n)] compounds have been obtained. The molecular structures of [(μ-2-abpy){Au(PPh(3))}(2)](CF(3)SO(3))(2) and [(μ-4-abpy){Au(PMe(3))}(2)](CF(3)SO(3))(2) have been confirmed by X-ray diffraction studies and feature linear gold(I) centers coordinated by pyridyl groups, and non-coordinated azo groups. In contrast the X-ray structure of [(2-abpy){Ag(CF(3)SO(3))(PPh(3))}(2)] shows tetracoordinated silver(I) centers involving chelating N-N coordination by pyridyl and azo nitrogen atoms. The gold(I) compounds with a long alkoxy chain do not behave as liquid crystals, and decompose before their melting point. The soluble gold(I) derivatives are photosensitive in solution and isomerize to the cis azo isomer under UV irradiation, returning photochemically or thermally to the most stable initial trans isomer. The silver(I) derivative [(2-abpy){Ag(CF(3)SO(3))(PPh(3))}(2)] also photoisomerizes in solution under UV irradiation, showing that its solid state structure, which would block isomerization by azo coordination, is easily broken. These processes have been monitored by UV-vis absorption and (1)H NMR spectroscopy. All these compounds are non-emissive in the solid state, even at 77 K.     

Protonation equilibria of nitrilotris(methylenephosphonato)-and ethylenediamine-tetrakis(methylenephosphonato)-complexes of scandium,yttrium, and lanthanoids

The protonation equilibria of nitrilotris(methylenephosphonic acid) (NTMP, H₆L) and ethylenediaminetetrakis(methylenephosphonic acid) (EDTMP, H₈L) complexes of scandium, yttrium, and lanthanoids have been studied potentiometrically at 25°C and at an ionic strength of 0.1 mol-dm^–3 KNO₃. The first protonation constants of NTMP complexes of lanthanoids, K _MHL , decrease with decreasing of the ionic radius of the lanthanoid [log K _MHL =7.82 (La³⁺) –6.90 (Lu³⁺)] and show a so-called Tetrad effect. The second protonation constants, K _{MH 2}L, change very little with the lanthanoid metal ions (logK _{MH 2}L=5.3–5.7). These results suggest that, in the first protonation process in ML, the proton attacks the nitrogen of NTMP rupturing the M-N of M(ntmp)^3–. The pattern of the change in the protonation constants of the EDTMP complexes with the atomic number of the lanthanoid is quite different from that of the NTMP complexes. This fact indicates that the manner of protonation of the EDTMP complexes differs from that of NTMP complexes. The protonation constants of yttrium complexes of NTMP and EDTMP agree with those of lanthanoid complexes, whereas those of scandium complexes deviate from the values predicted from its ionic radius.     

Functionalized thiosemicarbazone clusters of copper(I) and silver(I)

Reaction of [Cu(MeCN)(4)](+) with thiosemicarbazones bearing groups such as phenol, pyridine, or ferrocene gives tetranuclear or hexanuclear clusters with functional substituents; analogous air stable fluorescent clusters can also be prepared with Ag(I).     

N,S-donor acetamide ligand: silver (I) binding and test silver (I) extraction studies

Transition Metal Chemistry - Ligands bearing soft donors including N- and S- have found applications in selective metal recovery due to the ability to preferentially bind soft acceptors like Ag+....     

Bis(trimethylphosphine)silver(I) hexafluorophosphate

In the title two‐coordinate silver compound, [Ag(C₃­H₉­P)₂]­PF₆, the cation has crystallographically imposed mirror symmetry, and approximates very closely to m (D_3d) symmetry with fully staggered methyl groups in the solid state. The Ag atom has a nearly linear coordination geometry, with a P—Ag—P angle of 178.70 (4)°. The Ag—P bond lengths are 2.3746 (12) and 2.3783 (12) Å, which are ­significantly longer than the Au—P bond length of 2.304 (1) Å in the analogous two‐coordinate gold cation. The lack of intra­molecular steric effects within the present cations containing tri­methyl­phosphine (cone angle 118°), compared with those in known cations containing trimesityl­phosphine (cone angle 212°), provides a better comparison of M—P distances and thus more conclusive evidence that Au really is smaller than Ag.     

Thermal decomposition of silver(I) and mercury(I) anthranilates and salicyloaldoximates

The processes of thermal decomposition of silver(I) and mercury(I) anthranilates and salicyloaldoximates were studied. Thermal, chemical and X-ray analyses and infrared spectroscopy were used to determine the mechanisms of decomposition of these complexes. The factor determining the decomposition is the character of the Ag⁺ and Hg ₂ ²⁺ ions, which are easily reduced to free metals. The final reaction product of the compounds of silver is the pure metal; the compounds of mercury are volatilized completely when heated.