- New class of single-source precursors for the synthesis of main group-transition metal oxides: Heterobimetallic Pb-Mn β-dlketonates
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Heterometallic lead-manganese β-diketonates have been isolated in pure form by several synthetic methods that include solid-state and solution techniques. Two compounds with different Pb/Mn ratios, PbMn2(hfac) 6 (1) and PbMn(hfac)su
- Zhang, Haitao,Yang, Jen-Hsien,Shpanchenko, Roman V.,Abakumov, Artem M.,Hadermann, Joke,Clerac, Rodolphe,Dikarev, Evgeny V.
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- Syntheses of Dioxygenyl Salts by Photochemical Reactions in Liquid Anhydrous Hydrogen Fluoride: X-ray Crystal Structures of α- A nd β-O2Sn2F9, O2Sn2F9·0.9HF, O2GeF5·HF, and O2[Hg(HF)]4(SbF6)9
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By treating gaseous, liquid, or solid fluorides with UV-photolyzed O2/F2 mixtures and by treating solid oxides with UV-photolyzed F2 (or O2/F2 mixtures) in liquid anhydrous HF at ambient temperature, we investigated the possibility of the preparation of O2MIIIF4 (M = B, Fe, Co, Ag), O2MIVF5 (M = Ti, Sn, Pb), (O2)2MIVF6 (M = Ti, Ge, Sn, Pb, Pd, Ni, Mn), O2MIV2F9 (M = Sn), O2MVF6 (M = As, Sb, Au, Pt), O2MV2F11 (M = Pt), O2MVIF7 (M = Se), (O2)2MVIF8 (M = Mo, W), and O2MVIIF8 (M = I). The approach has been successful in the case of previously known O2BF4, O2MF6 (M = As, Sb, Au; Pt), O2GeF5, and (O2)2(Ti7F30). Novel compounds O2GeF5·HF, α-O2Sn2F9 (1-D), and the HF-solvated and nonsolvated forms of β-O2Sn2F9 (2-D) were synthesized and their crystal structures determined using single-crystal X-ray diffraction. The crystal structures of all of these materials arise from the condensation of octahedral MF6 (M = Ge, Sn) units. The anion in the crystal structure of O2GeF5·HF is comprised of infinite ([GeF5]-)∞ chains of GeF6 octahedra that share common vertices. The HF molecules and O2+ cations are located between the chains. The crystal structure of α-O2SnF9 (1-D) is constructed from [O2]+ cations and polymeric ([Sn2F9]-)∞ anions which appear as two parallel infinite chains comprised of SnF6 units, where each SnF6 unit of one chain is connected to a SnF6 unit of the second chain through a shared fluorine vertex. The single-crystal structure determination of [O2][Sn2F9]·0.9HF reveals that it is comprised of two-dimensional ([Sn2F9]-)∞ grids with [O2]+ cations and HF molecules located between them. The 2-D grids have a wavelike conformation. The ([Sn2F9]-)∞ layer contains both six- A nd seven-coordinated Sn(IV) atoms that are interconnected by bridging fluorine atoms. A new, more complex [O2]+ salt, O2[Hg(HF)]4[SbF6]9, was prepared. In its crystal structure, the Hg atoms bridge to SbF6 units to form a 3-D framework. The O2+ cations are located inside the voids while the HF molecules are bound to Hg atoms through the F atom. Attempts to prepare several chlorine analogues of O2+ fluorine salts (i.e., O2TiCl5 and O2MCl6 (M = Nb, Sb)) failed.
- Goreshnik, Evgeny,Mazej, Zoran
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- On the constitution of PbF4 with structure refinement of SnF4
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Colourless single crystals of SnF4 have been prepared heating powder samples of SnF4 in Pt-tubes (500°C, 20 d). Single crystals of PbF4 could be synthesized by pressure fluorination of 'PbF4-x' and sublimation in autoclaves. The fluorides crystallize isosructural in space group I4/mmm with SnF4: a = 404.42(4) pm; c = 792.41(9) pm; Z = 2 and PbF4: a = 425.36(8) pm; c = 806.4(1) pm; Z = 2 (Guinier-de Wolff data, Cu-Kα1). The parameters zF2 of both fluorides were refined from four-circle diffractometer data (Siemens AED 2) with SnF4: R1 = 1.5%; 1623 Io(Hkl) and PbF4: R1 = 1.0%; 777 Io(hkl) (SHELXL-93). The structures correspond to the supposition by Hoppe and Daehne from 1962. The Madelung Part of Lattice and Molecule Energy, MAPLE and MAPME, Mean Fictive Ionic Radii, MEFIR, and Effective Coordination Numbers, ECoN, are calculated. Johann Ambrosius Barth 1996.
- Bork,Hoppe
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p. 1557 - 1563
(2008/10/09)
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