Mercury Complexes Research Articles

The role of unconventional stacking interactions in the supramolecular assemblies of Hg(ii) coordination compounds

In this study, nine mercury(II) complexes of the composition [Hg(Ln)(X)2] (X = Cl, Br and I, n = 1–3), (L1 = 2-pyridine piconyl hydrazone); L2 = (2-acetylpyridine piconyl hydrazone) and L3 = (2-phenylpyridine piconyl hydrazone) are synthesized and spectroscopically characterized. Single-crystal X-ray crystallography showed that the molecular complexes can aggregate into larger entities depending upon the anion coordinated to the metal centre. Moreover, Hirshfeld surface (HS) analyses were employed to gain additional insight into interactions responsible for the packing of complexes 1–9. Quantitative examination of 2D fingerprint plots revealed, among others, the dominating participation of H⋯H and H⋯X interactions in the molecular packing. Moreover, C–H⋯X hydrogen bonds, π–π, and chelate-ring–π interactions are described and analysed by means of density functional theory (DFT) calculations since they play an important role in the construction of three-dimensional supramolecular frameworks. The influence of the halide on the energetic features of the assemblies has been also studied.

Content of Total Phenolics, Flavan-3-Ols and Proanthocyanidins, Oxidative Stability and Antioxidant Capacity of Chocolate During Storage.

Antioxidant (AO) capacity of chocolates with 27, 44 and 75% cocoa was assessed after production and during twelve months of storage by direct current (DC) polarographic assay, based on the decrease of anodic current caused by the formation of hydroxo-perhydroxyl mercury(II) complex (HPMC) in alkaline solutions of hydrogen peroxide at potentials of mercury oxidation, and two spectrophotometric assays. Relative antioxidant capacity index (RACI) was calculated by taking the average value of the AO assay (the sample mass in all assays was identical). Oxidative stability of chocolate fat was determined by differential scanning calorimetry. Measured parameters and RACI were correlated mutually and with the content of total phenols (Folin-Ciocalteu assay), flavan-3-ols (vanillin and p-dimethylaminocinnamaldehyde assay) and proanthocyanidins (modified Bate-Smith assay). During storage, the studied functional and health-related characteristics remained unchanged. Amongst applied AO assays, the DC polarographic one, whose validity was confirmed by two-way ANOVA and F-test, correlated most significantly with oxidative stability (oxidation onset temperature and induction time). In addition, principal component analysis was applied to characterise chocolate types.

Antimicrobial and toxicological evaluations of binuclear mercury(ii)bis(alkynyl) complexes containing oligothiophenes and bithiazoles

We investigated the antimicrobial activity of bis-(alkynyl)mercury(ii) complexes with oligothiophene and bithiazole linking units against MRSA and C. albicans, and their cytotoxicity was tested on NIH 3T3 cells.

Supramolecular adducts based on weak interactions between the trimeric Lewis acid complex (perfluoro-ortho-phenylene)mercury and polypnictogen complexes.

Reactions of the trinuclear Lewis acid perfluoro-ortho-phenylene)mercury [(o-HgC6F4)3] (1) with the polypnictogen complex [CpMo(CO)2(η(3)-P3)] (2) containing a cyclo-P3 ligand and the series of E2 complexes [{CpMo(CO)2}2(μ,η(2):η(2)-E2)] (E = P(3a), As(3b), Sb(3c), Bi(3d)) are reported. In all cases, the reaction products show very weak interactions between the En ligand complexes and the Lewis acid 1, as evidenced by their highly dynamic behaviour in solution and the formation of adducts in the solid state showing HgE contacts below the respective sum of the van der Waals radii. The complexes 2 (P3), 3a (P2) and 3b (As2) show interactions of only one pnictogen atom with all three Hg atoms of 1. The complex 3c (Sb2) forms two adducts with 1 showing either a side-on coordination of the Sb2 dumbbell towards Hg or an end-on coordination of both Sb atoms towards two independent molecules of 1. The Bi2 complex 3d shows an almost parallel alignment of the Bi2 dumbbell situated above the center of the planar Lewis acid 1. The arrangements of the E2 complex series towards 1 are rationalized with the help of electrostatic potential maps obtained by DFT calculations. Finally the structural characterizations of a new modification of the free Sb2 complex 3c, the Bi2 complex 3d, the starting material of its preparation [Bi{CpMo(CO)3}3] (4) and an unprecedented 'Cr4As5' cluster 5 are presented.

Structurally characterized bimetallic porphyrin complexes of Pb, Bi, Hg and Tl based on unusual coordination modes

This minireview highlights the unusual coordination geometries observed in bimetallic complexes of mercury, thallium, lead and bismuth. These bimetallic complexes remain scarce and through an analysis of their X-ray structures, the various structural features that favorise them will be underlined.

Synthesis and structural characterization of monomeric mercury(II) selenolate complexes derived from 2-phenylbenzamide ligands.

Monomeric Hg(II) selenolate complexes derived from 2-phenylbenzamide ligands were prepared by oxidative addition of diselenides [{C6H4(CONR2)Se}2, R = Me, Et, iPr] to elemental Hg and reductive cleavage of the Se–N bond of isoselenazolone derivatives [(NO2)C6H3(CONSe)R, (R = allyl, nbutyl)] followed by the treatment with HgCl2. The complexes have been characterized by multinuclear NMR (1H, 13C and 77Se) spectroscopy and mass spectrometry which suggest the monomeric form of these in solution. The molecular structures of diselenides [C6H4(CONR2)Se]2 and mercury selenolates [Hg{(NO2)C6H3(CONH-C3H5) Se}2], [Hg{C6H4(CONiPr2)Se}2] and [Hg{C6H4(CONMe2)Se}2] were established by a single crystal X-ray diffraction study. Diselenides show strong intramolecular non-bonded Se⋯O interactions, which are influenced by the nature of C(O)NR̲2 and decrease with the sterically bulky alkyl substituent (Se⋯O =2.823 Å for R = di-Me, 2.760 Å for R = allyl, and 3.157 Å for R = di-iPr). Mercury complexes derived from less bulky 2-phenyl-N,N-dialkylbenzamide ligands associated with poor or no intramolecular nonbonded Hg⋯O interactions (4.91 Å for R = di-Me, 4.199 Å for R = allyl) and instead strong intermolecular Hg⋯O [2.792(3) and 2.820(4) Å] for di-Me and allyl and Hg⋯Se [3.3212(5) and 3.4076(8) Å] interactions were observed which lead to a dimeric form in the crystals. On the other hand, the mercury complex derived from the sterically bulky diisopropyl amide ligand shows a strong intramolecular non-bonded Hg⋯O (2.860 Å) interaction, adopts linear geometry and exists as a monomer. Thermogravimetric analysis (TGA) of the mercury selenolate complexes revealed two-step decomposition which leads to the formation of HgSe. The mercury selenolate complex 3c derived from the sterically bulky 2-phenyl-N,Ndiisopropylbenzamide ligand decomposed to give HgSe in the range of 220-300 °C.

Structural and computational study of some new nano-structured Hg(ii) compounds: a combined X-ray, Hirshfeld surface and NBO analyses

Crystal structure, Hirshfeld surface, DFT and NBO analyses of two new distorted square-pyramidal mercury complexes are presented.

Enhanced two-photon excited fluorescence of mercury complexes with a conjugated ligand: Effect of the central metal ion

Based on the chelation of 6-phenyl-4′-(4-[4-(diphenylamino)styryl]phenyl)-2,2′-bipyridine (L) to Hg(II) ions, two luminescent coordination complexes HgBr2L (1) and HgI2L (2) were prepared. Compared with the free ligand, the complexes exhibit enhanced two-photon excited fluorescence and larger two-photon absorption cross-section values. Time-dependent density functional theory calculations were carried to investigate the influence of central metal ion on the characteristic of charge transition of the complexes. The results indicated that the complexation of the ligand with Hg(II) ion causes stronger intramolecular charge transfer, leading to enhanced two-photon absorption of the complexes.

Photoluminescent tetrahedral d10-metal Schiff base complexes exhibiting highly ordered mesomorphism

A series of four-coordinate d10-metal complexes of the type [ML2] {M=Zn, Cd, Hg; L=4-nitro-2-((octadecylimino)methyl)phenol}, incorporating a new N-alkylated bidentate [N,O]-donor salicylaldimine Schiff base ligand, has been synthesized and characterized by elemental analyses, FT-IR, UV–Vis, 1H NMR and FAB-mass spectroscopies. The ligand is non-mesomorphic and devoid of any photoluminescence. The zinc(II) and cadmium(II) complexes displayed highly ordered mesophases reminiscent of soft crystals. The phases have been characterized by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and powder X-ray diffraction (PXRD) studies. The complex of mercury(II) decomposed prior to melting. An orthogonal symmetry with a ‘herringbone’ array for the zinc complex and a primitive triclinic symmetry (p1) for the cadmium complex, respectively, has been proposed. The complexes exhibited fluorescence at room temperature, both in the solution and in the solid state, with emission maxima in the blue region. Density functional theory (DFT) calculations carried out using the gaussian 09 program at the B3LYP level revealed a distorted tetrahedral geometry around the metal center in all the complexes. Natural bond orbital (NBO) analysis suggested appreciable charge transfer from the ligand to the metal center in the complexes.

Structure, Bonding, and Stability of Mercury Complexes with Thiolate and Thioether Ligands from High-Resolution XANES Spectroscopy and First-Principles Calculations.

We present results obtained from high energy-resolution L3-edge XANES spectroscopy and first-principles calculations for the structure, bonding, and stability of mercury(II) complexes with thiolate and thioether ligands in crystalline compounds, aqueous solution, and macromolecular natural organic matter (NOM). Core-to-valence XANES features that vary in intensity differentiate with unprecedented sensitivity the number and identity of Hg ligands and the geometry of the ligand environment. Post-Hartree-Fock XANES calculations, coupled with natural population analysis, performed on MP2-optimized Hg[(SR)2···(RSR)n] complexes show that the shape, position, and number of electronic transitions observed at high energy-resolution are directly correlated to the Hg and S (l,m)-projected empty densities of states and occupations of the hybridized Hg 6s and 5d valence orbitals. Linear two-coordination, the most common coordination geometry in mercury chemistry, yields a sharp 2p to 6s + 5d electronic transition. This transition varies in intensity for Hg bonded to thiol groups in macromolecular NOM. The intensity variation is explained by contributions from next-nearest, low-charge, thioether-type RSR ligands at 3.0-3.3 Å from Hg. Thus, Hg in NOM has two strong bonds to thiol S and k additional weak Hg···S contacts, or 2 + k coordination. The calculated stabilization energy is -5 kcal/mol per RSR ligand. Detection of distant ligands beyond the first coordination shell requires precise measurement of, and comparison to, spectra of reference compounds as well as accurate calculation of spectra for representative molecular models. The combined experimental and theoretical approaches described here for Hg can be applied to other closed-shell atoms, such as Ag(I) and Au(I). To facilitate further calculation of XANES spectra, experimental data, a new crystallographic structure of a key mercury thioether complex, Cartesian coordinates of the computed models, and examples of input files are provided as Supporting Information .

Structure, photochromism and mesogenic property of mercury(II) complexes of 1-alkyl-2-(arylazo)imidazoles

Structure, photochromism and mesogenic property of mercury(II) complexes of 1-alkyl-2-(arylazo)imidazoles

Dimeric and polymeric mercury(II) complexes of 1-methyl-1,2,3,4-tetrazole-5-thiol: Synthesis, crystal structure, spectroscopic characterization, and thermal analyses

Two-dimensional coordination polymer of [Hg(μ3-mmtz)2]n (1) and centrosymmetric dinuclear complexes of {[H2en][Hg2(mmtz)4(μ-Br)2]} (2) and {[H2en][Hg2(mmtz)4(μ-I)2]} (3) (where Hmmtz is 1-methyl-1,2,3,4-tetrazole-5-thiol and en is ethylene diamine) were synthesized from the reaction of Hmmtz and en with HgCl2, HgBr2 and HgI2, respectively, in CH3OH. Complex 1 was also synthesized from the reaction of Hmmtz and en with HgX2 (X = OAc and SCN) in CH3OH. These three complexes were thoroughly characterized by elemental analysis (CHN), thermal gravimetric analysis (TGA), differential thermal analyses (DTA), infrared, UV–vis, 1H NMR, and luminescence spectroscopy, and their structures were determined by single-crystal X-ray diffraction.

Uranium, Cesium, and Mercury Leaching and Recovery from Cemented Radioactive Wastes in Sulfuric Acid and Iodide Media

The Canadian Nuclear Laboratories (CNL) is developing a long-term management strategy for its existing inventory of solid radioactive cemented wastes, which contain uranium, mercury, fission products, and a number of minor elements. The composition of the cemented radioactive waste poses significant impediments to the extraction and recovery of uranium using conventional technology. The goal of this research was to develop an innovative method for uranium, mercury and cesium recovery from surrogate radioactive cemented waste (SRCW). Leaching using sulfuric acid and saline media significantly improves the solubilization of the key elements from the SRCW. Increasing the NaCl concentration from 0.5 to 4 M increases the mercury solubilization from 82% to 96%. The sodium chloride forms a soluble mercury complex when mercury is present as HgO or metallic mercury but not with HgS that is found in 60 °C cured SRCW. Several leaching experiments were done using a sulfuric acid solution with KI to leach SRCW cured at 60 °C and/or aged for 30 months. Solubilization yields are above 97% for Cs and 98% for U and Hg. Leaching using sulfuric acid and KI improves the solubilization of Hg by oxidation of Hg0, as well as HgS, and form a mercury tetraiodide complex. Hg and Cs were selectively removed from the leachate prior to uranium recovery. It was found that U recovery from sulfuric leachate in iodide media using the resin Lewatit TP260 is very efficient. Considering these results, a process including effluent recirculation was applied. Improvements of solubilization due to the recycling of chemical reagents were observed during effluent recirculation.

Crystal structures of three mercury(II) complexes [HgCl2 L] where L is a bidentate chiral imine ligand.

The crystal structures of three complexes [HgCl2 L] were determined, namely, (S)-(+)-di-chlorido-[1-phenyl-N-(pyridin-2-yl-methyl-idene)ethyl-amine-κ(2) N,N']mercury(II), [HgCl2(C14H14N2)], (S)-(+)-di-chlorido-[1-(4-methyl-phen-yl)-N-(pyridin-2-yl-methyl-idene)ethyl-amine-κ(2) N,N']mercury(II), [HgCl2(C15H16N2)], and (1S,2S,3S,5R)-(+)-di-chlorido-[N-(pyridin-2-yl-methyl-idene)isopino-camph-eyl-amine-κ(2) N,N']mercury(II), [HgCl2(C16H22N2)]. The complexes consist of a bidentate chiral imine ligand coordinating to HgCl2 and crystallize with four independent mol-ecules in the first complex and two independent mol-ecules in the other two. The coordination geometry of mercury is tetra-hedral, with strong distortion towards a disphenoidal geometry, as a consequence of the imine bite angle being close to 70°. The Cl-Hg-Cl angles span a large range, 116.0 (2)-138.3 (3)°, which is related to the aggregation state in the crystals. For small Cl-Hg-Cl angles, complexes have a tendency to form dimers, via inter-molecular Hg⋯Cl contacts. These contacts become less significant in the third complex, which features the largest intra-molecular Cl-Hg-Cl angles.

Crystal structures and Hirshfeld surface analysis calculations of mercury(II) complexes with a diiminopyridine ligand

The reaction of a diiminopyridine ligand, N,N′-bis(phenyl(pyridin-2-yl)methylene)propane-1,3-diamine (L), with mercury(II) salts gave two complexes namely [Hg(L)Cl]·0.5[Hg2Cl6] (1) and [Hg(L)(μ-I)HgI3] (2), which were characterized by XRD, NMR and FTIR. The crystal structure of 1 consists of discrete units of [Hg(L)CI]+cations and [Hg2C16]2- anions in the ratio 2:1. The coordination of mercury in the cation is approximately square pyramidal (sp), the metal center is chelated in a tetradentate manner by the ligand and further coordinated by one chlorine atom. In 2 the packing can be described as units of μ-I-connected square pyramidal (sp) and tetrahedral Hg complexes. The sp coordination around the metal atom is defined by the N4 donor set of the ligand and one bridging iodide. The hydrogen–chlorine donor–accepter interactions in 1 stabilize an infinite 1-D chain; however, such interactions were not observed in 2. Analysis of their Hirshfeld surfaces indicates that the molecules in 1 and 2 are packed predominately by means of van der Waals forces, ‘edge to face’ aromatic ring packing and weak C–H··X donor-acceptor interactions.

Zinc and mercury complexes of benzil bis(4-methyl-3-thiosemicarbazone)

The ligand benzil bis(4-methyl-3-thiosemicarbazone), LMe2H4, reacts with zinc and mercury nitrates, both in the presence or in the absence of lithium hydroxide. Complexes containing a neutral or a doubly deprotonated ligand, depending on the reaction conditions, have been prepared. In all the complexes, the bis(thiosemicarbazone) acts as a N2S2 tetradentate ligand and in complex 4 probably also as a bridge through the sulfur atom leading to a dinuclear structure, while complex 3 is a monomer with a water molecule coordinated to the zinc atom in a penta-coordinated environment. Complexes 1 and 2 contain monodentate nitrato ligands in a hexa-coordinated structure, which is confirmed by the crystal structure of complex 2, [Hg(LMe2H4)(NO3)2]. The complexes have been thoroughly characterized by elemental analysis, mass spectrometry, FTIR and 1H, 13C and 199Hg NMR spectroscopy and in the case of complex 2, also by single crystal X-ray diffraction.

A comparison of solution and solid state coordination environments for calcium(II), zirconium(IV), cadmium(II) and mercury(II) complexes with dipicolinic acid and methylimidazole derivatives

Four new supramolecular compounds, (2-mimH)[Ca(pydcH)3][Ca(pydcH2)(pydc)(H2O)2]·4H2O (1), (1-mimH)2[Zr(pydc)3] (2), (2-mimH)2[Cd(pydc)2]·8H2O (3), and (2-mimH)2[Hg(pydc)2]·8H2O (4) [where pydcH2 = pyridine-2,6-dicarboxylic acid (dipicolinic acid), 1-mim = 1-methylimidazole, and 2-mim = 2-methylimidazole], have been synthesized and characterized by elemental analyses, spectroscopic techniques (IR, UV–vis, 1H NMR, and 13C NMR), thermal (TG/DTG/DTA) analysis as well as single-crystal X-ray diffraction. All four compounds are proton-transfer salts of the methylimidazolium cations and metal complex anions that crystallized from a solution of pyridine-2,6-dicarboxylic acid, methylimidazole, metal nitrates or chlorides as starting materials. The coordinating dicarboxylic acid is deprotonated at the carboxyl group and methylimidazole is protonated to balance the charge. In the crystal structures of 1–4, hydrogen bonding and π–π stacking play important roles. Water clusters are formed in 1, 3, and 4. The equilibrium constants of dipicolinic acid (pydc) and methylimidazole derivatives (1-mim and 2-mim), pydc-2-mim, pydc-1-mim proton-transfer systems as well as those of their complexes were investigated by a potentiometric pH titration method. The stoichiometries of most of the complex species in solution were very similar to the cited crystalline metal ion complexes.

Synthesis, Characterization, Crystal Structure, and Properties of a Mercury(Ii) Complex Containing Dmit Ligand and N,N’-Ethylidenedipyridium Cation

A new mercury(II) complex containing dmit ligand and biquaternary ammonium cation, DPyE[Hg(dmit)2] (1) (DPyE2+ = N,N’-ethylidenedipyridinium, dmit = 1,3-dithiol-2-thione-4,5-dithiolate), was synthesized and fully characterized by elemental analysis, IR, 1H-NMR, UV–Vis, TG, single crystal X-ray diffraction, and powder X-ray diffraction. Moreover, the electrochemical properties and conductivities of complex 1 were studied by cyclic voltammetry and four-probe AC technique, respectively. Complex 1 crystallizes in the monoclinic space group P 21/n with a = 8.1815(2) Å, b = 12.8701(5) Å, c = 23.2681(7) Å, β = 90.922(3)°, Z = 4, V = 2449.75(14) Å3, Dc = 2.114 g·cm–3. The crystal structure shows that the dihedral angle of two dmit ligands of [Hg(dmit)2]2– anion is closed to vertical, which results in the formation of a distorted HgS4 tetrahedral geometry. The S···S short contacts assemble [Hg(dmit)2]2– anions into 1D, 2D, and 3D supramolecular network. The DPyE2+ cations are located in the caves, providing additional stabilization to crystal packing via C–H···S hydrogen bonds to [Hg(dmit)2]2– anions. The crystal packing of 1 is characterized by face-to-face π-π contacts between DPyE2+ cations and [Hg(dmit)2]2– anions, which result in two orthogonally oriented and mixed stacking columns. These stacking columns interweave into a 2D network, which is further connected to a 3D network via interplanar S···S contacts. In addition, the temperature-dependent conductivity in the range of 50–300 K reveals semi-conducting properties of complex 1, and a room temperature conductivity of 1.53 × 10–3 S·cm–1 is observed.

Mixed-stack architecture and solvatomorphism of trimeric perfluoro-ortho-phenylene mercury complexes with dithieno[3,2-b:2′,3′-d]thiophene

The formation of the mixed-stack donor–acceptor complex of dithieno [3,2-b:2′,3′-d]thiophene (1) and trimeric perfluoro-ortho-phenylene mercury (I) has been investigated under different conditions. Two solvatomorphs – mixed-stack complexes with a 1:1 donor–acceptor ratio and different solvent molecules in the solid state (dichloromethane (2) and dichloroethane (3)) have been obtained and characterized by experimental methods (FT-IR spectroscopy, differential thermogravimetric analysis, and X-ray crystallography) and quantum-chemical calculations at the density functional theory level. The differences in the solid state packing, thermal stability and potential charge-transfer properties of 2 and 3 are discussed.

Differential Pulse Anodic Stripping Voltammetry for Mercury Determination

Abstact In the present work voltammetric investigations have been performed on HgCl2 aqueous solutions prepared from a Cz 9024 reagent. Carbon paste electrode (CPE), eriochrome black T modified carbon paste electrode (MCPE/EBT) and KCl 1M as background electrolyte, were involved within the experimental procedures. Cyclic voltammetry (CV) has been performed in order to compare the behaviour of the two electrodes in both K3[Fe(CN)6] and mercury calibration aqueous solution. Differential pulse anodic stripping voltammetry (DPASV) was used to determine the most suitable parameters for mercury determination. All experiments were performed at 25 ± 1 ℃, using an electrochemical cell with three-electrodes connected to an Autolab PG STAT 302N (Metrohm-Autolab) potentiostat that is equipped with Nova 1.11 software. The measured potential values were generated by using the silver chloride electrode (AgClE) as reference and a platinum wire electrode as auxiliary. A series of time depending equations for the pre-concentration and concentration steps were established, with the observation that a higher sensitivity can be obtained while increasing the pre-concentration time. DPASV were drawn using the CPE in 11.16 % coriander, as mercury complex, the voltamograms signals indicating mercury oxidation, with signal intensity increasing in time.