- Noble-gas difluoride complexes of mercury(II): The syntheses and structures of Hg(OTeF5)2·1.5NgF2 (Ng = Xe, Kr) and Hg(OTeF5)2
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The synthesis of high-purity Hg(OTeF5)2 has resulted in its structural characterization in the solid state by Raman spectroscopy and single-crystal X-ray diffraction (XRD) and in solution by 19F NMR spectroscopy. The crystal structure of Hg(OTeF5)2 (-173 C) consists of discrete Hg(OTeF5)2 units having gauche-conformations that interact through long Hg - -O and Hg - -F intramolecular contacts to give a chain structure. The Lewis acidity of Hg(OTeF5)2 toward NgF2 (Ng = Xe, Kr) was investigated in SO2ClF solvent and shown to form stable coordination complexes with NgF2 at -78 C. Both complexes were characterized by low-temperature Raman spectroscopy (-155 C) and single-crystal XRD. The complexes are isostructural and are formulated as Hg(OTeF5) 2·1.5NgF2. The Hg(OTeF5)2 units of Hg(OTeF5)2·1.5NgF2 also have gauche-conformations and are linked through bridging NgF2 molecules, also resulting in chain structures. These complexes represent the only examples of coordination compounds where NgF2 coordinates to mercury in a neutral covalent compound and the only example of mercury coordinated to KrF2. Moreover, the Hg(OTeF5)2·1. 5KrF2 complex is the only KrF2 complex known to contain a bridging KrF2 ligand. Energy-minimized gas-phase geometries and vibrational frequencies for the model compounds, [Hg(OTeF5) 2]3 and [Hg(OTeF5)2] 3·2NgF2, were obtained and provide good approximations of the local environments of Hg(OTeF5)2 and NgF2 in the crystal structures of Hg(OTeF5)2 and Hg(OTeF5)2·1.5NgF2. Assignments of the Raman spectra of Hg(OTeF5)2 and Hg(OTeF 5)2·1.5NgF2 are based on the calculated vibrational frequencies of the model compounds. Natural bond orbital analyses provided the associated bond orders, valencies, and natural population analysis charges.
- Debackere, John R.,Mercier, Helene P. A.,Schrobilgen, Gary J.
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- Study of the Ionic Conductivity Properties of the Solid Solution Hg1-xBixF2 + x.
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A solid solution Hg//1//-//xBi//xF//2// plus //x (0 less than x less than equivalent to 0. 40) has been prepared at 500 degree C in the HgF//2-BiF//3 56 system. The study of the transport properties shows that is is a good anionic conductor. The results are discussed in comparison with those previously obtained for the PbF//2-BiF//3 system.
- Chartier,Grannec,Reau,Hagenmuller,French
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- One dimensional group 12 metal undecafluoridoditantalates
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The reactions between group 12 metals and the acidic TaF5were studied in the anhydrous HF (aHF) solvent. We were able to prepare and characterize the first compounds containing metal M2+cations and undecafluoridodimetallate anions – M(Ta2F11)2(M?=?Cd, Hg) without the additional cations, anions or ligands included in the crystal structure. They both crystallize in P-1 space group with cell parameters a?=?9.1571(4)??, b?=?9.8750(3)??, c?=?10.9400(7) ?, α?=?94.389(4)°, β?=?113.124(5)°, γ?=?101.142(3)°, V?=?879.81(8) ?3, Z?=?2, T?=?150?K (Cd(Ta2F11)2) and a?=?9.1381(5)??, b?=?9.8613(6)??, c?=?11.4470(7)??, α?=?114.086(6)°, β?=?102.290(5)°, γ?=?100.398(5)°, V?=?877.84(11) ?3, Z?=?2, T?=?150?K (Hg(Ta2F11)2). Metal cations connected through two anions form chains along b axis. M(HF)2(TaF6)2.nHF (M?=?Cd, Hg) compounds were also prepared in the MF2/TaF5(M?=?Cd, Hg) system and their crystal structures were determined.
- Tav?ar, Ga?per,Goreshnik, Evgeny
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- Revealing the structural chemistry of the group 12 halide coordination compounds with 2,2′-bipyridine and 1,10-phenanthroline
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The coordination compounds of group 12 halides with 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen), 2[CdF2(bpy)2]·7H2O (1), [ZnI(bpy)2]+·I3 ? (2), [CdI2(bpy)2] (3), [Cd(SiF6)H2O(phen)2]·[Cd(H2O)2(phen)2]2+·F–·0.5(SiF6)2–·9H2O (4), [Hg(phen)3]2+·(SiF6)2–·5H2O (5), [ZnBr2(phen)2] (6), 6[Zn(phen)3]2+·12Br–·26H2O (7) and [ZnI(phen)2]+·I– (8), have been synthesized and characterized by X-ray crystallography, IR spectroscopy, elemental and thermal analysis. Structural investigations revealed that metal : ligand stoichiometry in the inner coordination sphere is 1 : 2 or 1 : 3. A diversity of intra- and intermolecular interactions exists in structures of 1–8, including the rare halogen?halogen and halogen?π interactions. The thermal and spectroscopic properties were correlated with the molecular structures of 1–8. Structural review of all currently known coordination compounds of group 12 halides with bpy and phen is presented.
- Swiatkowski, Marcin,Kruszynski, Rafal
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p. 642 - 675
(2017/02/05)
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- Probing the reactivity of the potent AgF2 oxidizer. Part 2: Inorganic compounds
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The reactivity of AgIIF2 towards forty two inorganic compounds containing oxo- and chloro- ligands, has been investigated. Five families of compounds were studied: (i) binary oxides of metals and nonmetals, (ii) ternary salts of inor
- Malinowski, Przemyslaw,Mazej, Zoran,Grochala, Wojciech
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p. 2608 - 2616
(2009/05/09)
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- Hg4OF6, the First Mercury Oxide Fluoride
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Hg4OF6 was observed at the first time as a product of the thermal decomposition of (O2)2Hg2F(SbF6)5. The pure compound has been obtained via solid state reaction of HgO and HgF2 as a vermilion, crystalline powder. Itcrystallizes hexagonally in the Ba4OCl6 type of structure (P6&3#mc (No. 186), a=774.57(1), c=600.75(1) pm, Z=2, Rietveld profile fitting, R&P#= 6.17%, R&wP#=8.00%).
- Mueller, Bernd G.,Klein, Wilhelm,Jansen, Martin
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- Contributions to the chemistry of brominetrifluoride. Part 2. Bis(pentafluorophenyl)bromonium cations with weak nucleophilic fluoroelementate anions
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BrF3 reacts with MII(C6F5)2 (M = Zn, Cd, Hg) in organic solvents independent of the stoichiometry under formation of C6F5BrF2. Bromonium compounds [(C6F5)2Br]+ [EFn+l]- (E = Sb, As, B) are formed in equimolar reactions if additionally Lewis-acids EFn are present. [(C6F5)2Br]+ [BF4]- results in quantitative yield independent of the stoichiometry of substrates if BrF3 reacts with the Lewis-acidic aryl transfer reagent (C6F5)2BF. The molecular structure of the bromonium compounds [(C6F5)2Br]+ [BF4]- and [(C6F5)2Br]+ [AsF6]- can be interpreted in terms of two asymmetric hypervalent bonds at bromine(III). In solution the electrophilicity of Br(III) in [(C6F5)2Br]+ [EFn+l]- is responsible for the strong dependence of the 19F NMR shift values from the nucleophilicity of the solvent. Gauthier-Villars.
- Frohn,Giesen,Welting,Henkel
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p. 841 - 853
(2008/10/08)
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- INTERACTION OF XENON DIFLUORIDE WITH ORGANOMERCURY COMPOUNDS
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XeF2 is shown to react with organomercury compounds, R2Hg (R=PhCC, p-MeOC6H4, p-Me2NC6H4, p-EtO2CC6H4 and PhCH2), with cleavage of the C-Hg bond.The products of the reaction are the following: Xe, RHgF (or RHgF/HgF2 mixture; for R=benzyl RHgF undergoes
- Butin, K. P.,Kiselev, Yu. M.,Magdesieva, T. V.,Reutov, O. A.
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p. 127 - 134
(2007/10/02)
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