Reaction Of HgCl Research Articles

Silver(I) and mercury(II) complexes with N, N′-bis(acetylacetone)-1 R,2 R-diaminocyclohexane ligands exhibiting three different coordination modes

Treatment of AgNO 3 with one equiv. of N, N′-bis(acetylacetone)-1 R,2 R-diaminocyclohexane ( L) afforded a mononuclear complex [Ag(η 2- L)NO 3] ( 1) in which the central silver(I) atom adopts a distorted trigonal planar geometry by coordinating two carbon atoms of the methane moieties of the ligand and one oxygen atom of the NO 3 − group. Interaction of CF 3COOAg with one equiv. of L produced a one-dimensional coordination polymer [Ag 2(μ- L)(CF 3CO 2) 2] n ( 2). Each silver(I) in 2 exhibits highly distorted square planar coordination geometry that connects one oxygen atom of L and one neighboring Ag atom with the Ag⋯Ag interactions. Reaction of HgCl 2 with one equiv. of L resulted in the formation of one-dimensional [{Hg(μ-Cl)Cl} 2(μ-η 1- L)] n ( 3) with a C-coordinated dinuclear mercury(II) chloride moiety being linked by L.

Formation and structural characterization of mercury complexes from Te(R)CH 2SiMe 3 (R = Ph, CH 2SiMe 3) and HgCl 2

The reaction of HgCl 2 and Te(R)CH 2SiMe 3 [R = CH 2SiMe 3 ( 1), Ph ( 2)] in ethanol yielded a mononuclear complex [HgCl 2{Te(R)CH 2SiMe 3} 2] (R = Ph, 3a; R = CH 2SiMe 3, 3b). The recrystallization of 3a or 3b from CH 2Cl 2 produced a dinuclear complex [Hg 2Cl 2(μ-Cl) 2{Te(R)CH 2SiMe 3} 2] (R = Ph, 4a; R = CH 2SiMe 3, 4b). When 3a was dissolved in CH 2Cl 2, the solvent quickly removed, and the solid recrystallized from EtOH, a stable ionic [HgCl{Te(Ph)CH 2SiMe 3} 3]Cl·2EtOH ( 5a·2EtOH) was obtained. Crystals of [HgCl 2{Te(CH 2SiMe) 2}]·2HgCl 2·CH 2Cl 2 ( 6b·2HgCl 2·CH 2Cl 2) were obtained from the CH 2Cl 2 solution of 3b upon prolonged standing. The complex formation was monitored by 125Te-, and 199Hg NMR spectroscopy, and the crystal structures of the complexes were determined by single crystal X-ray crystallography.

Coordination geometry isomerism induced by N–H⋯Cl, C–H⋯Cl, C–H⋯N, C–H⋯π and π⋯π supramolecular interactions in mercury(II) complexes with tripyridylimidazole chelating ligands

Reaction of HgCl 2 with trans-(±)2-(2,5-di(pyridin-2-yl)-4,5-dihydro-1 H-imidazol-4-yl)pyridine ( L1) and cis-(±)-(phenyl(2,4,5-tri(pyridin-2-yl)-4,5-dihydroimidazol-1- yl)methanone ( L2) gives mononuclear complexes, 1 and 2. In these complexes L1 and L2 behave as tridentate and bidentate chelating ligands, giving distorted trigonal bipyramidal and tetrahedral coordination geometries, respectively. X-ray diffraction studies revealed a series of N–H⋯Cl, C–H⋯Cl, C–H⋯N and C–H⋯π interactions in 1 giving a 3D network, and N–H⋯Cl, C–H⋯Cl, C–H⋯π and π⋯π interactions in 2 giving a 2D network in the crystal lattice. Since both ligands should have a similar binding capacity to the mercury ions, the variations observed for coordination number and geometry should be a consequence of supramolecular stabilizing effects.

Mercury(II)–methylene blue interactions: Complexation and metallate formation

Reactions of HgX 2 (X = Cl, Br, I) with methylene blue (MB) chloride dihydrate and the reaction of HgCl 2 with MB nitrate dihydrate have been undertaken in an attempt to prepare metal derivatives of MB. The products were characterized by elemental analysis, UV–Vis, IR, 1H NMR spectroscopy and X-ray crystallography. The reaction of HgCl 2 with MB chloride dihydrate and subsequent crystallization in a DMF/H 2O mixture yielded the products ( 1 and 2) with different crystal morphologies. The structure of complex 1 represents the first structural report of a complex of MB with any metal ion. The efficacy of MB to act as a ligand in spite of its cationic nature is thus demonstrated. The structure of 1 comprises a distorted tetrahedral geometry around Hg(II); the coordination valencies being provided by three chloride ions and a MB cation. The structure of 2 is a salt consisting of an HgCl 4 2 - anion and two MB cations. The reaction of HgI 2 and HgBr 2 with MB chloride dihydrate yielded salts 3 and 4 with Hg 2 X 6 2 - (X = Br or I) anions and MB cations. A mixed salt 5, whose anions comprise mercury(II), chloride and nitrate species resulted from the reaction between HgCl 2 with MB nitrate dihydrate. The reaction of Hg 2F 2 with MB chloride dihydrate and the crystallization of the resulting product 6 in aqueous DMF yielded crystals of (MB) 2HgCl 4 · H 2O.

Syntheses and Crystal Structures of Xylyl-Bridged NO2S2-Donor Macrocycles and Binuclear Mercury(II) Complex

Isomeric series ofdilinked NO 2 S 2 macrocycles (L 2 : para-, L 3 : meta- and L 4 : ortho-linked) capable ofbinuclear complexing ability were prepared from its monomeric analog L 1 in reasonable yields except ortho-type reaction, which led to mixture due to the formation of monomer-type macrocyclic quaternary ammonium bromide L 5 . Moreover, L 2 (as 2HNO 3 form) and L 5 were confirmed by an X-ray crystallography. Reaction of HgCl 2 with L 2 yielded a binuclear complex [Hg 2 (L 2 )Cl 4 ]. In the complex, each mercury(II) has a distorted tetrahedral environment made up of S and N donors from an exodentate L 2 and two coordinated Cl atoms.

LP/LIF study of the formation and consumption of mercury (I) chloride: Kinetics of mercury chlorination

The laser photolysis/laser induced fluorescence (LP/LIF) technique has been applied to studies of gas-phase mercury (Hg) chlorination. Mercury (I) chloride (HgCl) was been detected via LIF at 272 nm from reactions of elemental Hg with Cl atoms generated from the 193 nm photolysis of carbon tetrachloride. While the formation of HgCl was too fast to be observed on millisecond time scales, the kinetics of the consumption of HgCl have been determined at temperatures characteristic of post-combustion conditions. Rate coefficients and Arrhenius parameters for the reaction of HgCl with Cl 2, HCl and Cl atoms were determined. The reaction of HgCl with Cl 2 was the fastest reaction studied, while the reaction of HgCl with HCl was the only reaction to show any measurable temperature dependence. Estimates of the rate coefficient for the reaction Hg + Cl → HgCl were determined using a modeling approach. Comparisons of these new measurements with model predictions are discussed.

A novel biosensor for mercuric ions based on motor proteins

We explored the potential of contractile proteins, actin and myosin, as biosensors of solutions containing mercuric ions. We demonstrate that the reaction of HgCl 2 with myosin rapidly inhibits actin-activated myosin ATPase activity. Mercuric ions inhibit the in vitro analog of contraction, namely the ATP-initiated superprecipitation of the reconstituted actomyosin complex. Hg reduces both the rate and extent of this reaction. Direct observation of the propulsive movement of actin filaments (10 nm in diameter and 1 μm long) in a motility assay driven by a proteolytic fragment of myosin (heavy meromyosin or HMM) is also inhibited by mercuric ions. Thus, we have demonstrated the biochemical, biophysical and nanotechnological basis of what may prove to be a useful nano-device.

Syntheses and structures of highly hindered N-functionalised alkyl and amido group 12 complexes MR 2 (M=Zn, Cd, and Hg), [MRCl] 2 (M=Zn and Hg)

The reaction of MCl 2 (M=Zn, Cd and Hg) with Li(2-(C(SiMe 3) 2)(6-Me–C 5H 3N)), [Li(MeR)], affords mononuclear metal(II) alkyls. These, in the solid state, show intramolecular M–N interactions in their four-membered chelate rings, which progressively weaken down the series, the C–M–C angles becoming more open (〈M–N〉= 2.30(2), 2.52(2), 2.913(4) Å, C–M–C=160.7(2), 168.5(2), 180(-)°). Alkylmercury chloride complexes have been prepared by the reaction of HgCl 2 with [Li(MeR)], Li(2-(C(SiMe 3) 2)(C 5H 4N)), [Li(HR)], or Li(2-(NSiMe 3)(6-Me–C 5H 3N)), [Li(mpsa)], or from the redistribution reaction of the dialkyl (or amido) mercury complex with HgCl 2. The alkylmercury chloride complexes are dimeric or polymeric in nature with near-linear 2-coordination; (Hg–Cl=2.329(5), 2.318(4), 2.272(8) Å, Cl–Hg–C(N)=175.0(4), 174.7(4), 175.6(5)°). Cd(2-(CH(SiMe 3))(6-Me-C 5H 3N)) 2(tmen), prepared from the reaction of Li(2-(CH(SiMe 3))(6-Me–C 5H 3N)) and CdCl 2 in the presence of tmen, has also been structurally authenticated as the rac isomer with the ipso protons directed towards the tmen.

Arene-mercury complexes stabilized aluminum and gallium chloride: synthesis and structural characterization.

Reaction of HgCl(2) with 2 equiv of MCl(3) in an aromatic solvent yields Hg(arene)(2)(MCl(4))(2) where, arene = C(6)H(5)Me, M = Al (1), Ga (2); arene = C(6)H(5)Et, M = Al (3) and Ga (4); o-C(6)H(4)Me(2), M = Al (5), Ga (6); C(6)H(3)-1,2,3-Me(3), M = Al (7) and Ga (8). The solid-state structures of compounds 1-5 and 7 have been determined by X-ray crystallography. In the solid state, compounds 1-4 and 7 exist as neutral complexes in which two arenes are bound to the mercury, and the MCl(3) groups are bound through bridging chlorides to the mercury; compound 5 exists as a cation-anion pair [Hg(o-C(6)H(4)Me(2))(2)(AlCl(4))][AlCl(4)]. However, in solution compounds 1-8 all exist as neutral complexes. The structures of Hg(arene)(2)(AlCl(4))(2) and [Hg(arene)(2)(AlCl(4))](+) have been determined by DFT calculations [B3LYP level] to facilitate the assignment of the (13)C CPMAS NMR spectra and are in good agreement with the X-ray diffraction structures of compounds 1 and 5. Reaction of HgCl(2) with MCl(3) in benzene, m-xylene, and p-xylene results in the formation of liquid clathrates whose spectroscopic characterization is consistent with ionic structures, [Hg(arene)(2)(MCl(4))][MCl(4)]. The calculated energy difference between Hg(C(6)H(5)Me)(2)(AlCl(4))(2) and [Hg(C(6)H(5)Me)(2)(AlCl(4))][AlCl(4)] is discussed with respect to the structure of compound 5 in the solid state versus solution state and the proposed speciation in the liquid clathrates.

Synthesis and X-ray structure of the first chloro-bridged thiourea mercury(II) complex [C 6H 5C(OCH 3)NC(S)N(C 2H 5) 2HgCl 2] 2

The complex bis{(μ-chloro)-chloro-[( N-diethylaminothiocarbonyl)benzimido- O-methyl ester- S]mercury(II)} was prepared by the reaction of HgCl 2 with N-(diethylaminothiocarbonyl)benzimido- O-methyl ester. The compound has been characterised by FAB mass spectrometry, IR spectroscopy and NMR spectroscopy. The dimeric structure was established crystallographically: space group P-1, a=9.3296(4), b=9.5298(2), c=11.4615(2) Å, α=71.9930(10), β=88.8600(10), γ=65.0150(10)°, Z=1. Each mercury atom takes a tetragonal distorted geometry and is coordinated by two bridging chloride atoms, one terminal chloride atom and one thiocarbonyl sulfur atom of the ligand. The compound is the first example of a chloro-bridged mercury(II) complex of a ligand with a thiourea moiety; the bridge can be designated as symmetric.

Di-μ-chloro-bis[(2-ammoniobenzenethiolato-S)chloromercury(II)

The title compound, [Hg 2 Cl 4 (C 6 H 7 NS) 2 ], was obtained from the reaction of HgCl 2 with benzothiazole and studied by X-ray diffraction and IR spectroscopy. The molecule is centrosymmetric, with Hg-μ-Cl distances of 2.720(1) and 2.976(1) A. The 2-aminobenzenethiol ligand (existing in a zwitterionic form) is bonded to mercury through the S atom, with an Hg-S distance of 2.340 (2) A. There are N-H...Cl hydrogen bonds involving the bridging Cl atoms, as well as a bifurcated hydrogen bond involving the terminal Cl atoms.

Synthesis, structure and properties of the polychalcogenides [M 4Te 12] 4− (M=Cd, Hg)

The cluster anions, [M 4Te 12] 4− (MCd, Hg) are reported. (Et 4N) 4[Cd 4Te 12] ( I) was prepared by the reaction of CdI 2, K 2Te 2 and Et 4NBr in a 2:3:2 molar ratio, in DMF. I crystallizes in the orthorhombic space group Cmca (No. 64) with a = 15.482(5), b = 22.563(4), c = 18.027(4) Å, V = 6297(5) Å 3 and Z = 4. The black rectangular platelet crystals of (Me 4N) 4[Hg 4Te 12] ( II) were obtained from the reaction of HgCl 2 and K 2Te in a 2:5 molar ratio in DMF. II crystallizes in the monoclinic space group P2 1/ n (No. 14) with a = 10.324(3), b = 21.851(6), c = 11.125(4) Å, β = 110.63(3)°, V = 2348(3) Å 3 and Z = 2. [M 4Te 12] 4− is a cluster with two Te 2−, two Te 2 2− and two Te 3 2− ligands connecting a planar array of four tetrahedral M 2+ metal centers. Its shape may be described as a basket, consisting of an {M 4(Te 2) 2Te 2} core with two side Te 3 2− handles. The average M-Te and Te-Te distances are 2.85(8) and 2.74(2) Å for I, respectively, and 2.86(12) and 2.73(1) Å for II, respectively. The far-IR spectra show two absorptions at 173 and 160 cm −1 for I and at 167 and 148 cm −1 for II. Thermal gravimetric analysis data are reported.

Reactivity of carbonyl complexes containing MoHg bonds; reaction of tin(II) halides with [Mo(CO) 3(NN)(HgX)(X)] (NN = bpy, phen, dmp); crystal structure of [Mo(CO) 3(dmp)(HgCl)(Cl)

Reaction of HgCl 2 with [Mo(CO) 4(dmp)] (dmp = 2,9-dimethyl-1,10-phenanthroline) gives the heterobimetallic compound [Mo(CO) 3(dmp)(HgCl)(Cl)] ( I), which gives rise to a new compound [Mo(CO) 3(dmp)(HgCl)(Cl)] · 1 2 (CH 3) 2CO ( II) in acetone solution at low temperature. The crystal structure of I has been solved and the compound shown to be a capped trigonal prism containing MoHgCl and MoCl bonds. The reactions of the above and related heteronuclear complexes [Mo(CO) 3(NN)(HgX)(X)] [X = Cl, Br; NN = 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen)] with tin(II) halides were studied. No insertion of the latter into the metalmetal or metalhalogen bonds were observed, with only bimetallic tricarbonyl complexes containing MoHg bonds being isolated.

Synthesis, electrochemical behaviour and structural characterization of the mercury complex [Hg([18]aneN 6)]·(HgCl 4)

Reaction of HgCl 2, in slight excess of 1 molar equivalent of the ligand ([18]aneN 6) in water, produces a colourless solution containing [Hg([18]aneN 6)](HgCl 4). The X-ray structure of this complex shows that the six nitrogen donor atoms of the macrocycle surround the mercury(II) atom in a distorted trigonal prismatic coordination. Cyclic voltammetry of [Hg([18]ane)] 2+ shows a chemically reversible reduction at a HDM electrode, with E 1 2 = −0.293 V vs S.C.E. at pH 9.37 and a scan rate of 200 mV s −1. The global oxidation-reduction process involves two electrons and two protons.

Mercury complexes with one-dimensional chain structures. Syntheses and crystal structures of polymeric (acetato)(mercaptopyridinato)mercury, bis(mercaptopyridinato)mercury and bis(thioxodiphenylphosphinomethyl)mercury

Reaction of Hg(OAc) 2 , OAc − CH 3 CO2 − , with 1 equiv of mercaptopyridine, C 5 H 5 NS, in CH 2 Cl 2 at 22 o C gives the compound Hg(OAc)(C 5 H 4 NS) in 82% yield. Hg atoms in 1 are bridged by the C 5 H 4 NS ligand to form a one-dimensional chain complex. Reaction of Hg(OAc) 2 with 2 equiv of C 5 H 5 NS in CH 2 Cl 2 at 22 o C produces the complex Hg(C 5 H 4 NS) 2 in 92% yield. 1 can be converted to 2 by the addition of 1 equiv of C 5 H 5 NS. Reaction of HgCl 2 with 2 equiv of Li(MTP), MTP=CH 2 PPh 2 S, in THF at -78 o C gives Hg(MTP) 2 in 65% yield. The structures of 1-3 were determined by single-crystal X-ray diffraction

Formation of an asymmetric RhHgRh bridged complex

Reaction of HgCl 2 with [Rh 2(μ-Cl)(CO) 2(μ-CO)(μ-dppm) 2]Cl (dppm = bis(diphenylphosphino)methane) gives [Rh 2Cl 3(μ-HgCl)(CO) 2(μ-dppm) 2] in which only one Rh is oxidised by insertion into a HgCl bond, and which consequently contains an unusual asymmetric RhHgRh bridge.