Mechanism of extraction of the palladium(ii) thiocyanate complex by polyether foam

The mechanism of sorption of the palladium(II) thiocyanate complex by polyether-type Polyurethane foam has been investigated. At low thiocyanate concentration, palladium is most likely extracted as Pd(SCN)(2). The results obtained in the presence of enough thiocyanate for formation of the Pd(SCN)(4)(2-) complex are in disagreement with several possible mechanisms for sorption of the anionic metal complex by the foam, such as adsorption, solvent extraction, ligand addition or exchange, and weak or strong base anion-exchange. The extraction of Pd(SCN)(4)(2-) at high pH increased in the order Li(+)< Na(+) < Cs(+)< Rb(+) < K(+)< NH(4)(+) which is in good relation with the "cation-chelation" mechanism. This mechanism was also found predominant in the extraction of Pd(SCN)(4)(2-) complex from hydrochloric acid solutions.     

The cation-chelation mechanism of metal-ion sorption by polyurethanes

The mechanism of sorption of ions by polyurethanes has been investigated through detailed studies of the extraction of cobalt(II) thiocyanate and the salts of several organic acids. Polyether-based polyurethanes. particularly those containing poly(ethylene oxide), were found to be distinctly superior to polyesters in the sorption of salts and performed much better than might be expected by analogy with monomeric liquid solvents. The results were judged to be inconsistent with several possible mechanisms, including adsorption, solvent extraction, weak or strong base anion-exchange, and complexation of metal anions by the polymer. A new proposal, termed the cation chelation mechanism (CCM), was advanced to account for the observations. In this view, a number of cations (including those of the alkali metals, alkaline earth metals, some transition metals, NH(+)(4), RNH(+)(3) and perhaps H(3)O(+)) may be multiply complexed (chelated) by portions of the polymer, thus facilitating the sorption of accompanying anions. As predicted by the mechanism, moderately strong and selective complexation of several cations was observed to occur with the following order of selectivity: Li(+) < Na(+) < Cs(+) < Rb(+) < K(+) approximately NH(+)(4) < Ag(+) approximately Tl(+) < Ba(2+) < Hg(2+) < Pb(2+). Such behaviour parallels that known for many crown and non-cyclic polyethers and is therefore identified with the polyether portions of the polymer, which are thought to adopt helical conformations surrounding the complexed cations. The cation-chelation mechanism may be widely applicable to the sorption of ions of several types by polyether-based polyurethanes, particularly when large, hydrophobic anions (such as anionic metal complexes) are accompanied by an excess of chelatable cations.     

Indirect Determination of CTMAB with Sodium Chloride and Ammonium Thiocyanate by Floatation and Separation of Zinc

Cetyl-trimethylammoniumbromide(CTMAB)isaveryusefulcationicsurfactant,sothestudyondeterminationofCTMABassumesgreatimportance.AsmallamountofCTMABisgenerallydeterminedbyspectrophotometrybasingCTMABcombineswithtriazidetoformcoloredbinaryion-associationcomplex1-3.However,thosemethodsofdeterminationofCTMABhavedisadvantagesofsmalllinearrange,needofspecialreagent,determinationinbaseenvironment,etc.Inthispaper,indirectdeterminationofCTMABwithNaClandNH4SCNbyfloatationandseparationofZn(II…     

New metal-organic frameworks with large cavities: selective sorption and desorption of solvent molecules

Five novel transition metal complexes [Cd(II) (3)(tpba-2)(2)(SCN)(6)].6 THF.3 H(2)O (1), [Cu(II) (3)(tpba-2)(2)(SCN)(6)].6 THF.3 H(2)O (2), [Ni(II) (3)(tpba-2)(2)(SCN)(6)].6 THF.3 H(2)O (3), [Cd(II) (2)(tpba-2)(SCN)(3)]ClO(4) (4), [Cu(I) (3)(SCN)(6)(H(3)tpba-2)] (5) [TPBA-2 = N',N',N'-tris(pyrid-2-ylmethyl)-1,3,5-benzenetricarboxamide, THF=tetrahydrofuran] were obtained by reactions of the corresponding transition metal salts with TPBA-2 ligand in the presence of NH(4)SCN using layering or solvothermal method, respectively. The results of X-ray crystallographic analysis showed that complexes 1, 2 and 3 are isostructural and have the same 2D honeycomb network structure with Kagomé lattice, in which all the M(II) (M = Cd, Cu, Ni) atoms are six-coordinated, and the TPBA-2 ligands adopt cis,cis,cis conformation while the thiocyanate anions act as terminal ligands. Capsule-like motifs are found in 1, 2 and 3, in which six THF molecules are hosted, and the results of XPRD and solid-state (13)C NMR spectral measurements showed that the compound 1 can selectively desorb and adsorb THF molecules occurring along with the re-establishment of its crystallinity. In contrast to 1, 2 and 3, complex 4 has different 2D network structure, resulting from TPBA-2 ligands with cis,trans,trans conformation, thiocyanate anions serving as end-to-end bridging ligands, and the incomplete replacement of perchlorate anions, which further link the 2D layers into 3D framework by the hydrogen bonds. In complex 5, the Cu(II) atoms are reduced to Cu(I) during the process of solvothermal reaction, and the Cu(I) atoms are connected by thiocyanate anions to form a 3D porous framework, in which the protonated TPBA-2 ligands are hosted in the cavities as templates.     

Reengineering of a fluorescent zinc sensor protein yields the first genetically encoded cadmium probe

Introduction of a (Cys)(4) metal binding site at the dimerization interface of two fluorescent protein domains yields a chelating FRET sensor protein that shows a 2500-fold selectivity for Cd(2+) over Zn(2+) by taking advantage of their different ionic radii.     

Metal ion-binding properties of 1-methyl-4-aminobenzimidazole (=9-methyl-1,3-dideazaadenine) and 1,4-dimethylbenzimidazole (=6,9-dimethyl-1,3-dideazapurine). quantification of the steric effect of the 6-amino group on metal ion binding at the N7 site of the adenine residue

The stability constants of the 1:1 complexes formed between Mg(2+), Ca(2+), Sr(2+), Ba(2+), Mn(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), or Cd(2+) (=M(2+)) and 1-methyl-4-aminobenzimidazole (MABI) or 1,4-dimethylbenzimidazole (DMBI) were determined by potentiometric pH titrations in aqueous solution (25 degrees C; I = 0.5 M, NaNO(3)). Some of the stability constants were also measured by UV spectrophotometry. The acidity constants of the species H(2)(MABI)(2+) and H(DMBI)(+) were determined by the same methods, some twice. Comparison of the stability constants of the M(MABI)(2+) and M(DMBI)(2+) complexes with those calculated from log versus p straight-line plots, which were established previously for sterically unhindered benzimidazole-type ligands (=L), reveals that the stabilities of the M(MABI)(2+) and M(DMBI)(2+) complexes are significantly reduced due to steric effects of the C4 substituents on metal ion binding at N3. This effect is more pronounced in the M(DMBI)(2+) complexes. Considering the steric equivalence of methyl and (noncoordinating) amino groups (as they occur in adenines), it is concluded that the same extent of steric inhibition by the (C6)NH(2) group is to be expected on metal ion binding at N7 with adenine derivatives. The basicity of the amino group in MABI is significantly higher than in its corresponding adenine derivative. Indeed, it is concluded that in the M(MABI)(2+) complexes chelate formation involving the amino group occurs to some extent. The formation degrees of these "closed" species are calculated; they vary for the complexes of Mn(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), or Cd(2+) between about 50 and 90%. The stability of the M(MABI)(2+) and M(DMBI)(2+) complexes with the alkaline earth ions is very low but unaffected by the C4 substituent; this probably indicates that in these instances outersphere complexes (with a water molecule between N3 and the metal ion) are formed.     

The extraction and determination of thiocyanate complexes by use of polyurethane foam

Metal thiocyanate solutions were extracted with polyether-type polyurethane foam and the metal contents determined by X-ray fluorescence. Iron, cobalt and zinc were extracted individually and collectively from 3.0M NH(4)Cl and 1.0M NH(4)SCN solutions. Similarly platinum and palladium could be simultaneously extracted from 0.12MNH(4)SCN and 5.0MNH(4)Cl for subsequent determination. The metal extractions were more than 95% complete and the determination of one metal was not affected by the presence of the others.     

Extraction of palladium with tri-isobutylphosphine sulphide (cyanex 471) in toluene from chloride solutions containing thiocyanate

The extraction of PD(II) by tri-isobutylphosphine sulphide, TIBPS (Cyanex 47 1x), in toluene from aqueous chloride solutions (containing small amounts of thiocyanate) has been investigated. The extraction is enhanced by the presence of thiocyanate, owing to formation of mixed-ligand Pd(II)-Cl(-)-SCN(-)-TIBPS complexes. Analysis of the metal distribution suggests the formation of PdCl(SCN).TIBPS, PdCl(SCN).2TIBPS, Pd(SCN)(2).TIBPS and Pd(SCN)(2).2TIBPS in the organic phase. The equilibrium constants are logK(111) =9.56, logK(112) =12.70, logK(121) =14.73 and logK(122) =17.17, respectively. The ultraviolet absorption spectra of the organic phase support the hypothesis of formation of mixed-ligand complexes.     

Synthesis and characterization of quasi-two-coordinate transition metal dithiolates M(SAr*)2 (M = Cr, Mn, Fe, Co, Ni, Zn; Ar* = C6H3-2,6(C6H2-2,4,6-Pri3)2

A sequence of first row transition metal(II) dithiolates M(SAr)(2) (M = Cr(1), Mn(2), Fe(3), Co(4), Ni(5) and Zn(6); Ar = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-Pr(i)(3))(2)) has been synthesized and characterized. Compounds 1-5 were obtained by the reaction of two equiv of LiSAr with a metal dihalide, whereas 6 was obtained by treatment of ZnMe(2) with 2 equiv of HSAr. They were characterized by spectroscopy, magnetic measurements, and X-ray crystallography. The dithiolates 1, 2, and 4-6 possess linear or nearly linear SMS units with further interactions between M and two ipso carbons from C(6)H(2)-2,4,6-Pr(i)(3) rings. The iron species 3, however, has a bent geometry, two different Fe-S distances, and an interaction between iron and one ipso carbon of a flanking ring. The secondary M-C interactions vary in strength in the sequence Cr(2+) approximately Fe(2+) > Co(2+) approximately Ni(2+) > Mn(2+) approximately Zn(2+) such that the manganese and zinc compounds have essentially two coordination but the chromium and iron complexes are quasi four and three coordinate, respectively. The geometric distortions in the iron species 3 suggested that the structure represents the initial stage of a rearrangement into a sandwich structure involving metal-aryl ring coordination. The bent structure of 3 probably also precludes the observation of free ion magnetism of Fe(2+) recently reported for Fe{C(SiMe(3))(3)}(2). DFT calculations on the model compounds M(SPh)(2) (M = Cr-Ni) support the higher tendency of the iron species to distort its geometry.     

Structural and electronic characterization of the complexes obtained by the interaction between bare and hydrated first-row transition-metal ions (Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+)) and glycine

The complexes formed by the simplest amino acid, glycine, with different bare and hydrated metal ions (Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+)) were studied in the gas phase and in solvent in order to give better insight into the field of the metal ion-biological ligand interactions. The effects of the size and charge of each cation on the organization of the surrounding water molecules were analyzed. Results in the gas phase showed that the zwitterion of glycine is the form present in the most stable complexes of all ions and that it usually gives rise to an eta(2)O,O coordination type. After the addition of solvation sphere, a resulting octahedral arrangement was found around Ni(2+), Co(2+), and Fe(2+), ions in their high-spin states, whereas the bipyramidal-trigonal (Mn(2+) and Zn(2+)) or square-pyramidal (Cu(2+)) geometries were observed for the other metal species, according to glycine behaves as bi- or monodentate ligand. Despite the fact that the zwitterionic structure is in the ground conformation in solution, its complexes in water are less stable than those obtained from the canonical form. Binding energy values decrease in the order Cu(2+) > Ni(2+) > Zn(2+) approximately Co(2+) > Fe(2+) > Mn(2+) and Cu(2+) > Ni(2+) > Mn(2+) approximately Zn(2+) > Fe(2+) > Co(2+) for M(2+)-Gly and Gly-M(2+) (H(2)O)(n) complexes, respectively. The nature of the metal ion-ligand bonds was examined by using natural bond order and charge decomposition analyses.     

Quantum chemical studies of mononuclear zinc species of hydration and hydrolysis

Optimal geometries, charge distributions, bond analysis, changes of Gibbs free energy, entropies and enthalpies of hydration, and hydrolysis reactions for mononuclear species of Zn(2+) including hydrated and hydrolysis complexes were investigated using quantum chemical calculations in the gas phase. Optimized geometrical structures showed that the stable hydrated and hydrolysis zinc species without outer-sphere water molecules were Zn(H(2)O)(6)(2+), Zn(OH)(H(2)O)(3)(+), Zn(OH)(2)(H(2)O)(2), Zn(OH)(3)(-), and Zn(OH)(4)(2-). Results of NPA (Natural Population Analysis) indicated that the charge on the Zn atom of the hydrated ions decreased but the charge on the zinc atom of the hydrolysis species increased with the increase of inner-sphere water molecules. NBO (Natural Bond Orbital) analyses demonstrated that hydrated and hydrolysis species of zinc were mainly electrostatic bonding compounds. Calculations of reaction energies indicated that inner-sphere water molecules became more unfavorable as the hydrolysis increased. Stepwise hydrolysis equilibrium constants decreased successively and the order remained unchanged when the inner-sphere dehydration occurred.     

Ultrasonic and Raman Scattering Spectroscopy of Zinc Thiocyanate Complexes in Water at 25<Superscript>∘</Superscript>C: Kinetics of Complex Formation Determined by Multivariate Analysis

Advances have been made recently in broadening the accessible ultrasonic absorption frequency range and improving the detectability of minor species present in solution using Raman spectroscopy. Development of chemometric techniques in these areas needs to keep pace with the improvement of these experimental methods. Refinements in the analysis of ultrasonic and Raman data based on multivariable least squares and factor analysis, respectively, are examined to investigate the kinetics of zinc thiocyanate complex formation in water. Analysis of ultrasonic absorption relaxation spectra verified that the observed process in aqueous Zn(SCN)₂ involves substitution of water from the first coordination shell of Zn²⁺. Use of a multivariable least-squares error surface is described that enhances the reliability of assigned frequencies of ultrasonic absorption maxima. Factor analysis of Raman scattering data provided direct evidence that at least four complex species, such as Zn(SCN)⁺ and Zn(SCN)₂, are simultaneously present in the aqueous zinc thiocyanate solutions.     

Adsorption of metal halides from ethanol solutions by a 3-n-propylpyridiniumsilsesquioxane chloride-coated silica gel surface

3-n-propylpyridiniumsilsesquioxane chloride polymer, abbreviated as SiPy+Cl-, was used to coat a porous silica gel, SiO2, surface to form the chemically modified solid SiO2/SiPy+Cl-. The resulting polymer film was well adhered to the surface and presented an ion exchange capacity of 0.74 mmol g(-1). Metal halides, MClz [M=Fe(III), Cu(II), and Zn(II)], were adsorbed by the modified solid from ethanol solutions as neutral species by forming the surface anionic complexes described by the equation: mSiO2/SiPy+Cl-+ MClz <=> (SiO2/SiPy+)m[MCl(z+m)]m-, where the [MCl(z+m)]m- species adsorbed on the surface are FeCl4-, ZnCl4(2-), and CuCl4(2-). Accurate estimates of the specific sorption capacities and the heterogeneous stability constants of the immobilized metal complexes were determined with the aid of computational procedures.     

Competitive Substitution and Electron Transfer in Reactions between Haloamminegold(III) and Halocyanoaurate(III) Complexes and Thiocyanate

Kinetics for reactions between thiocyanate and trans-Au(CN)(2)Cl(2)(-), trans-Au(CN)(2)Br(2)(-), and trans-Au(NH(3))(2)Cl(2)(+) in an acidic, 1.00 M perchlorate aqueous medium have been studied by use of conventional and diode-array UV/vis spectroscopy and high-pressure and sequential-mixing stopped-flow spectrophotometry. Initial, rapid formation of mixed halide-thiocyanate complexes of gold(III) is followed by slower reduction to Au(CN)(2)(-) and Au(NH(3))(2)(+), respectively. This is an intermolecular process, involving attack on the complex by outer-sphere thiocyanate. Second-order rate constants at 25.0 degrees C for reduction of trans-Au(CN)(2)XSCN(-) are (6.9 +/- 1.1) x 10(4) M(-)(1) s(-)(1) for X = Cl and (3.1 +/- 0.7) x 10(3) M(-)(1) s(-)(1) for X = Br. For reduction of trans-Au(CN)(2)(SCN)(2)(-) the second-order rate constant at 25.0 degrees C is (3.1 +/- 0.1) x 10(2) M(-)(1) s(-)(1) and the activation parameters are DeltaH() = (55 +/- 3) x 10(2) kJ mol(-)(1), DeltaS() = (-17.8 +/- 0.8) J K(-)(1) mol(-)(1), and DeltaV() = (-4.6 +/- 0.5) cm(3) mol(-)(1). The activation volume for substitution of one chloride on trans-Au(NH(3))(2)Cl(2)(+) is (-4.5 +/- 0.5) cm(3) mol(-)(1), and that for reduction of trans-Au(NH(3))(2)(SCN)(2)(+) (4.6 +/- 0.9) cm(3) mol(-)(1). The presence of pi-back-bonding cyanide ligands stabilizes the transition states for both substitution and reductive elimination reactions compared to ammine. In particular, complexes trans-Au(CN)(2)XSCN(-) with an unsymmetric electron distribution along the X-Au-SCN axis are reduced rapidly. The observed entropies and volumes of activation reflect large differences in the transition states for the reductive elimination and substitution processes, respectively, the former being more loosely bound, more sensitive to solvational changes, and probably not involving any large changes in the inner coordination sphere. A transition state with an S-S interaction between attacking and coordinated thiocyanate is suggested for the reduction. The stability constants for formation of the very short-lived complex trans-Au(CN)(2)(SCN)(2)(-) from trans-Au(CN)(2)X(SCN)(-) (X = Cl, Br) by replacement of halide by thiocyanate prior to reduction can be calculated from the redox kinetics data to be K(Cl,2) = (3.8 +/- 0.8) x 10(4) and K(Br,2) = (1.1 +/- 0.4) x 10(2).     

A novel alpha-helix-liked metallohelicate series and their structural adjustments for the isomorphous substitution

A novel metallohelical motif is well designed and synthesized by mimicking the alpha-helical fold structure of protein. The 1D helical structures of [Cd(CH2(COO)2)(SC(NH2)2)2]n (I) and [Zn(CH2(COO)2) (SC(NH2)2)2]n (II) are primarily induced and stabilized by the multiple long-range intrahelix hydrogen bonds. Malonate dianion acts as a bidentate ligand coordinated with metal ions to form the backbone of the helix, and thiourea molecules that bend into the helical turn are involved in the intrahelix hydrogen-bond system. The metal ion occupations in the helix of I and II can be freely substituted by simply controlling the initial ratio of those two metal ions. Single crystals of three mixed metal ion complexes of [Cd0.77Zn0.23(CH2(COO)2)(SC(NH2)2)2]n (III), [Cd0.50Zn0.50(CH2(COO)2)(SC(NH2)2)2]n (IV), and [Cd0.21Zn0.79(CH2(COO)2)(SC(NH2)2)2]n (V) were synthesized from systems with an initial Cd/Zn mole ratio of 1:1 for III, 1:2 for IV, and 1:8 for V. They are isomorphous as confirmed by X-ray characterization. When the metal ion is substituted, the multiple intrahelix hydrogen interaction motifs of the coordination polymer structure are self-adjusted to sustain their 1D helical motifs.     

EXAFS study of Zn sorption mechanisms on hydrous ferric oxide over extended reaction time

The sorption species and coordination environment of zinc sorbed on to hydrous ferric oxide (HFO) did not change for aging times up to six months. At an initial concentration of 10(4-) M, Zn formed innersphere surface complexes on the surface of HFO. Zn was tetrahedrally coordinated with oxygen atoms at ZnO bond distance of approximately 1.94-1.97 A with coordination number of approximately 3.8-4.7. In the second shell Zn appeared to be coordinated with Fe with a bond distance of approximately 3.42-3.49 A. At an initial concentration of 10(3-) M, both innersphere and polynuclear complexes were feasible sorption products. The first shell was tetrahedrally coordinated with about four oxygen atoms at a bond distance of 1.96 A. The second shell could be attributed to either ZnFe or ZnZn correlations with almost the same bond distance of 3.42-3.44 A.     

Aroylhydrazone derivative as fluorescent sensor for highly selective recognition of Zn2+ ions: syntheses, characterization, crystal structures and spectroscopic properties

A new Zn(2+) fluorescent chemosensor N'-(3,5-di-tert-butylsalicylidene)-2-hydroxybenzoylhydrazine (H(3)L(1)) and its complexes [Zn(HL(1))C(2)H(5)OH](∞) (1) and [Cu(HL(1))(H(2)O)]CH(3)OH (2) have been synthesized and characterized in terms of their crystal structures, absorption and emission spectra. H(3)L(1) displays high selectivity for Zn(2+) over Na(+), K(+), Mg(2+), Ca(2+) and other transition metal ions in Tris-HCl buffer solution (pH = 7.13, EtOH-H(2)O = 8?:?2 v/v). To obtain insight into the relation between the structure and selectivity, a similar ligand 3,5-di-tert-butylsalicylidene benzoylhydrazine (H(2)L(2)), which lacks the hydroxyl group substituent in salicyloyl hydrazide compared with H(3)L(1), and its complex [Zn(2)(HL(2))(2)(CH(3)COO)(2)(C(2)H(5)OH)] (3), [Co(L(2))(2)][Co(DMF)(4)(C(2)H(5)OH)(H(2)O)] (4), [Fe(HL(2))(2)]Cl·2CH(3)OH (5), have also been investigated as a reference. H(3)L(1) exhibits improved selectivity for Zn(2+) compared to H(2)L(2). The findings indicate that the hydroxyl group substituent exerts an effect on the spectroscopic properties, complex structures and selectivity of the fluorescent sensor.     

Coordination properties of new bis(1,4,7-triazacyclononane) ligands: a highly active dizinc complex in phosphate diester hydrolysis

The synthesis and characterization of three new bis([9]aneN(3)) ligands, containing respectively 2,2'-bipyridine (L(1)), 1,10-phenanthroline (L(2)), and quinoxaline (L(3)) moieties linking the two macrocyclic units, are reported. Proton binding and Cu(II), Zn(II), Cd(II), and Pb(II) coordination with L(1)-L(3) have been studied by potentiometric titrations and, for L(1) and L(2), by spectrophotometric UV-vis measurements in aqueous solutions. All ligands can give stable mono- and dinuclear complexes. In the case of L(1), trinuclear Cu(II) complexes are also formed. The stability constants and structural features of the formed complexes are strongly affected by the different architecture and binding properties of the spacers bridging the two [9]aneN(3) units. In the case of the L(1) and L(2) mononuclear complexes, the metal is coordinated by the three donors of one [9]aneN(3) moiety; in the [ML(2)](2+) complexes, however, the phenanthroline nitrogens are also involved in metal binding. Finally, in the [ML(3)](2+) complexes both macrocyclic units, at a short distance from each other, can be involved in metal coordination, giving rise to sandwich complexes. In the binuclear complexes each metal ion is generally coordinated by one [9]aneN(3) unit. In L(1), however, the dipyridine nitrogens can also act as a potential binding site for metals. The dinuclear complexes show a marked tendency to form mono-, di-, and, in some cases, trihydroxo species in aqueous solutions. The resulting M-OH functions may behave as nucleophiles in hydrolytic reactions. The hydrolysis rate of bis(p-nitrophenyl)phosphate (BNPP) was measured in aqueous solution at 308.1 K in the presence of the L(2) and L(3) dinuclear Zn(II) complexes. Both the L(2) complexes [Zn(2)L(2)(OH)(2)](2+) and [Zn(2)L(2)(OH)(3)](+) and the L(3) complex [Zn(2)L(3)(OH)(3)](+) promote BNPP hydrolysis. The [Zn(2)L(3)(OH)(3)](+) complex is ca. 2 orders of magnitude more active than the L(2) complexes, due both to the short distance between the metal centers in [Zn(2)L(3)(OH)(3)](+), which could allow a bridging interaction of the phosphate ester, and to the simultaneous presence of single-metal bound nucleophilic Zn-OH functions. These structural features are substantially corroborated by semiempirical PM3 calculations carried out on the mono-, di-, and trihydroxo species of the L(3) dizinc complex.     

Formation of melamium adducts by pyrolysis of thiourea or melamine/NH4 Cl mixtures

Pyrolysis of prominent precursor compounds for the synthesis of carbon nitride type materials (e.g., melamine, thiourea) have been studied in detail. Molecular adducts containing monoprotonated melamium C(6)N(11)H(10)(+) and melaminium HC(3)N(3)(NH(2))(3)(+) ions, respectively, have been identified as intermediates. The adduct C(6)N(11)H(10)Cl·0.5NH(4)Cl was obtained by the reaction of melamine C(3)N(3)(NH(2))(3) with NH(4)Cl at 450 °C. During the pyrolysis of thiourea, guanidinium thiocyanate was initially formed and subsequently the melamium thiocyanate melamine adduct C(6)N(11)H(10)SCN·2C(3)N(3)(NH(2))(3) was isolated at 300 °C. A second melaminium thiocyanate melamine adduct with the formula HC(3)N(3)(NH(2))(3)SCN·2C(3)N(3)(NH(2))(3) represents an intermediary reaction product that is best accessible at low pressures. The crystal structures of the compounds were solved by single-crystal XRD. Unequivocal proton localization at the C(6)N(11)H(10)(+) ion was established. A typical intramolecular and interannular hydrogen bridge and other characteristic hydrogen-bonding motifs were identified. Additionally, the adducts were investigated by solid-state NMR spectroscopy. Our study provides detailed insight into the thermal condensation of thiourea by identifying and characterizing key intermediates involved in the condensation process leading to carbon nitride type materials. Furthermore, factors promoting the formation of melamium adduct phases over melem are discussed.     

Complexation behaviour and stability of Schiff bases in aqueous solution. The case of an acyclic diimino(amino) diphenol and its reduced triamine derivative

The copper(II), nickel(II), and zinc(II) complexes of the acyclic Schiff base H(2)L(A), obtained by [1 + 2] condensation of 1,2-ethanediamine,N-(2-aminoethyl)-N-methyl with 3-ethoxy-2-hydroxybenzaldehyde, and of H(2)L(B), the reduced derivative of H(2)L(A), were prepared and their properties studied by IR, NMR and SEM-EDS. In these complexes, the metal ion is always located in the coordination chamber of the ligand delimited by two phenol oxygens and nitrogen atoms (either aminic or iminic). The coordination behaviour of H(2)L(A) and H(2)L(B) towards H(+), Cu(2+), Ni(2+) and Zn(2+) in aqueous solution at 298 K and mu = 0.1 mol dm(-3) (Na)ClO(4) was also studied by potentiometric, NMR and UV-VIS measurements. In particular, potentiometric equilibrium studies indicate that H(2)L(A) is not stable enough to have a pH range in which it is the sole species in aqueous solution. In such a solution, the Schiff base forms over a limited pH range, between 6 and 10, with a maximum formation percentage at pH approximately 9. In addition, the involvement of imine nitrogens in the complexes markedly stabilises the azomethylene linkage, so that the metal complexes of H(2)L(A), particularly those of copper(II), are the species largely prevailing in solutions with pH >3.5. The stability constants of the complexes formed by metal ions with H(2)L(A) and H(2)L(B) follow the order Cu(2+) > Ni(2+) > Zn(2+); distribution plots show that copper(II) gives complexes more stable with H(2)L(A), whereas Ni(2+) and Zn(2+) prefer the reduced ligand, H(2)L(B).