7783-63-3Relevant academic research and scientific papers
Anion packing, hole filling, and HF solvation in A2(HF) nB12F12 and K2(HF)TiF6 (A = K, Cs)
Peryshkov, Dmitry V.,Friedemann, Roland,Goreshnik, Evgeny,Mazej, Zoran,Seppelt, Konrad,Strauss, Steven H.
, p. 118 - 127 (2013)
The crystal structures of three new HF solvates of fluoroanion salts of alkali metal ions are reported, K2(HF)TiF6, K 2(HF)3B12F12, and Cs 2(HF)B12F12. The anion packing in K 2(HF)TiF6 (P21/m) is distorted cubic close-packed with Ti?Ti distances that range from 5.717(1) to 7.394(1) (average 6.18). Half of the K+ ions are in Td holes and half are in Oh holes (i.e., this is a distorted version of the Cs2S structure). Each HF molecule is bonded to a K+ ion in the Oh holes (KF(H) = 2.679(5)) and also weakly interacts with two other K+ ions in adjacent Oh holes (K?F(H) = 3.238(2)). The anion packing in K2(HF)3B 12F12 (Fm3?m) is simple cubic. The (B12 centroid)?(B12 centroid) distance (??? distance) is 7.242, and disordered K2(μ-HF)3 2+ cations occupy each cube. The anion packing in Cs 2(HF)B12F12 (P21/c) is distorted hexagonal close-packed with ??? distances that range from 7.217 to 9.408 (average 8.304). The HF molecule bridges Cs+ ions in adjacent Oh holes, forming infinite Cs+(μ-HF)Cs +(μ-HF) chains. The other half of the Cs+ ions are in Td holes, displaced nearly 1 from the center of those holes. This structure is similar to the distorted Ni2In structure exhibited by Cs2(H2O)B12F12. The new results are used to compare and contrast the strength of M-F(H) interactions with M-F interactions involving F atoms from fluoroanions as well as the solid-state packing of icosahedral B12F122- anions and octahedral MF62- anions in alkali-metal salts, both with and without the inclusion of weakly-basic HF solvent molecules.
Guanidinium Perfluoridotitanate(IV) Compounds: Structural Determination of an Oligomeric [Ti6F27]3– Anion, and an Example of a Mixed-Anion Salt Containing Two Different Fluoridotitanate(IV) Anions
Shlyapnikov, Igor M.,Goreshnik, Evgeny A.,Mazej, Zoran
, p. 5246 - 5257 (2018)
Chemical reactions between guanidinium carbonate or guanidinium chloride and titanium tetrafluoride in anhydrous hydrogen fluoride (aHF) were studied. The obtained products were recrystallized from saturated HF, SO2 and CH3CN solutions. Single-crystal growths resulted in the detection of seven perfluoridotitanate(IV) compounds, which were structurally characterized. Three of them correspond to the phases obtained as the main products of the synthesis in aHF, i.e., [C(NH2)3]2[TiF6], [C(NH2)3]4[Ti4F20], and [C(NH2)3][Ti2F9]. When the guanidinium salt/TiF4 molar ratios were greater than 1:2, the resulting products were only sparingly soluble or completely insoluble in aHF. Therefore, single-crystal growths were attempted from other aprotic solvents (SO2 and CH3CN). Single crystals of [C(NH2)3]3[Ti6F27]·SO2 were detected in the case of the former and [C(NH2)3]4[H3O]4[Ti4F20][TiF5]4 in the case of the latter. The presence of [H3O]+ can be explained by a contamination with traces of H2O, which is protonated in the superacid aHF. The same reason applies to the formation of the by-products [H5O2]4[Ti8F36] and β-[H3O][Ti2F9]. The crystal structures of the new guanidinium-perfluoridotitanate(IV) compounds consist of oligomeric [Ti4F20]4–, [Ti6F27]3– and [Ti8F36]4–, as well as polymeric ([TiF5]–)∞ and ([Ti2F9]–)∞ perfluoridotitanate(IV) anions. The hexameric [Ti6F27]3– anion with a trigonal prismatic geometry was structurally determined for the first time. The crystal-structure determination of the [C(NH2)3]4[H3O]4[Ti4F20][TiF5]4 revealed the first example of a mixed-anion perfluoridotitanate(IV) compound containing two different perfluoridotitanate(IV) anions, i.e., oligomeric [Ti4F20]4– and 1-D polymeric ([TiF5]–)∞ anions. The crystal structure of the guanidinium hydrogen difluoride salt [C(NH2)3][HF2] is also reported.
19F NMR method for evaluation of the donor site basicity and coordination modes of chelating ligands in the reaction of α-picolinic acid and its derivatives with titanium tetrafluoride
Il'In,Tyuremnov
, p. 1330 - 1334 (2013)
It has been shown by the example of TiF4 complexes with α-picolinic acid (C5H5NCOOH, picH) and its esters (picEt and picSiMe3) in CH3CN that the 19F NMR chemical shifts can be used for estimating the basic properties of nonequivalent donor sites of chelating ligands. TiF4 reacts with picEt to form adducts: the TiF4(η2-picEt) chelate and trans-TiF 4(picEt)2. The reaction of TiF4 with an equimolar amount of picH yields the cis-TiF4 (η2-picH) complex with three nonequivalent fluorine positions. The introduction of a ligand excess leads to a change in the chemical shifts of the fluoro complex, which is interpreted to be due to the formation of H-bonded complexes TiF 4(η2-picH.picH). The introduction of Et3N, which binds protons, shifts the equilibrium toward the [TiF4(η 2-pic)]- anion. The reaction of TiF4 with picSiMe3 occurs in an essentially different way. The major species in solution is the [(μ-F)(μ-OOpic)2(TiF3) 2]- dimer. Its possible isomeric structures are discussed. On the basis of comparison of the chemical shifts of the fluorine atoms trans to the oxygen and nitrogen atoms of the chelate ligand, the conclusion has been drawn that the basicity of the chelate donor sites increases in the series (η2-picEt)TiF4 2-picH)TiF 4 2-pic)TiF4]- and that for all the complexes, the basicity of the nitrogen atom of the chelate is higher than that of the oxygen atom.
Crystal structures and raman spectra of imidazolium poly[perfluorotitanate(IV)] salts containing the [TiF6]2-, ([Ti2F9]-)∞, and [Ti 2F11]3- and the New [Ti4F 20]4- and [Ti5F23]3- anions
Shlyapnikov, Igor M.,Mercier, Helene P. A.,Goreshnik, Evgeny A.,Schrobilgen, Gary J.,Mazej, Zoran
, p. 8315 - 8326 (2013)
Reactions between imidazole (Im, C3H4N2) and TiF4 in anhydrous hydrogen fluoride (aHF) in different molar ratios have yielded [ImH]2[TiF6]·2HF, [ImH] 3[Ti2F11], [ImH]4[Ti 4F20], [ImH]3[Ti5F23], and [ImH][Ti2F9] upon crystallization. All five structures were characterized by low-temperature single-crystal X-ray diffraction. The single-crystal Raman spectra of [ImH]4[Ti4F20], [ImH]3[Ti5F23], and [ImH][Ti2F 9] were also recorded and assigned. In the crystal structure of [ImH]2[TiF6]·2HF, two HF molecules are coordinated to each [TiF6]2- anion by means of strong F-H···F hydrogen bonds. The [Ti2F 11]3- anion of [ImH]3[Ti2F 11] results from association of two TiF6 octahedra through a common fluorine vertex. Three crystallographically independent [Ti 2F11]3- anions, which have distinct geometries and orientations, are hydrogen-bonded to the [ImH]+ cations. The [ImH]4[Ti4F20] salt crystallized in two crystal modifications at low (α-phase, 200 K) and ambient (β-phase, 298 K) temperatures. The tetrameric [Ti4F20]4- anion of [ImH]4[Ti4F20] consists of rings of four TiF6 octahedra, which each share two cis-fluorine vertices, whereas the pentameric [Ti5F23]3- anion of [ImH] 3[Ti5F23] results from association of five TiF6 units, where four of the TiF6 octahedra share two cis-vertices, forming a tetrameric ring as in [Ti4F 20]4-, and the fifth TiF6 unit shares three fluorine vertices with three TiF6 units of the tetrameric ring. The [ImH][Ti2F9] salt also crystallizes in two crystal modifications at low (α-phase, 200 K) and high (β-phase, 298 K) temperatures and contains polymeric ([Ti2F9] -)∞ anions, which appear as two parallel infinite zigzag chains comprised of TiF6 units, where each TiF6 unit of one chain is connected to a TiF6 unit of the second chain through a shared fluorine vertex. Quantum-chemical calculations at the B3LYP/SDDALL level of theory were used to arrive at the gas-phase geometries and vibrational frequencies of the [Ti4F20]4- and [Ti5F23]3- anions, which aided in the assignment of the experimental vibrational frequencies of the anion series.
THE EQUILIBIRUM GEOMETRY AND FREQUENCIES OF THE VIBRATIONS OF THE TITANIUM TETRAFLUORIDE MILECULE
Girichev, G. V.,Petrov, V. M.,Giricheva, N. I.,Krasnov, K. S.
, p. 45 - 49 (1982)
The structure of the TiF4 molecule has been studied by gaseous electron diffraction at a temperature of 689 +/- 20 deg K.Simultaneous treatment of the data, obtained at two temperatures (689 and 475 deg K) , in the harmonic approximation gave the value of the equilibirum internuclear distance reh(Ti-F) = 1.745(3) Angstroem, the complete force field, and the frequencies of the vibrations: ν1 = 695(20), ν2 = 179(8), ν3 = 787(5), n4 = 225(20) cm-1.The force constants obtained are equal to the values obtained by the simultaneous treatment of the spectral and electron diffraction data.
Syntheses and the crystal chemistry of the perfluoridotitanate(IV) compounds templated with ethylenediamine and melamine
Shlyapnikov, Igor M.,Goreshnik, Evgeny A.,Mazej, Zoran
, p. 255 - 262 (2019)
Chemical reactions between ethane-1,2-diamine [C2H4(NH2)2; ethylenediamine, abbr. en] and 1,3,5-triazine-2,4,6-triamine [C3H6N6; melamine, abbr. mel], with titanium tetrafluoride (TiF4) were carried out in liquid anhydrous hydrogen fluoride (aHF). The latter acted in a dual role: as a reagent and as a solvent. The n(en): n(TiF4) = 2:1, 1:1, 1:3, 1:4, and n(mel): n(TiF4) = 2:1, 1:1, 1:2, 1:3, 1:4 M ratios were studied. Crystallizations of the products from the saturated HF solutions yielded single crystals of [enH2]F2·2HF, previously known [enH2][TiF6] and three new perfluoridotitanate(IV) salts, i.e., [enH2][TiF6]·HF, [enH2]0.5[TiF5] and [melH2][TiF6]·HF. Their crystal structures were determined including the crystal structure of the low-temperature modification of [enH2][TiF6]. The [enH2]0.5[TiF5] phase represents the first example of a structurally characterized perfluoridotitanate(IV) compound with a double charged cation, where instead of the usual octahedral [TiF6]2? monomer, another kind of anion is present, i.e., polymeric chain-like ([TiF5]?)∞ anion. The reactions in en/TiF4/HF and mel/TiF4/aHF systems are not selective enough to enable syntheses of individual [enH2]2+ and [melH2]2+ perfluoridotitanates(IV) in large quantities.
Poly[perfluorotitanate(IV)] salts of [H3O]+, Cs +1, [Me4N]+, and [Ph4P]+ and about the existence of an isolated [Ti2F9]- anion in the solid state
Mazej, Zoran,Goreshnik, Evgeny
, p. 6918 - 6923 (2009)
The increase In the size of monocatlons (A+) does not favor the formation of [Ti2F9]- against [Ti 4F18]2- salts (with isolated [Ti 2F9]- or [Tis
Fluorination of anatase TiO2 towards titanium oxyfluoride TiOF2: A novel synthesis approach and proof of the Li-insertion mechanism
Louvain,Karkar,El-Ghozzi,Bonnet,Guerin,Willmann
, p. 15308 - 15315 (2014)
The reactivity of pure molecular fluorine F2 allows the creation of new materials with unique electrochemical properties. We demonstrate that titanium oxyfluoride TiOF2 can be obtained under molecular fluorine from anatase titanium oxide TiO2, while the fluorination of rutile TiO2 leads only to pure fluoride form TiF4. Contrary to most fluorides, TiOF2 is air-stable and hydrolyses poorly under humid conditions. Such a stability makes it possible for TiOF2 to be studied as an electrode material in Li-ion secondary battery systems. It shows the capacity as high as 220 mA h g-1 and good cyclability at high current rates at an average potential of 2.3 V vs. Li+/Li. At such a potential, only Li+ insertion occurs, as proven by in operando XRD/electrochemistry experiments. the Partner Organisations 2014.
Crystal structures of phases observed in [H3O]+/M2+/[SbF6]?system (M?=?Mg, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Cd)
Mazej, Zoran,Goreshnik, Evgeny
, p. 82 - 88 (2016/12/14)
The reactions between the MO (M?=?Be, Mg, Ca, Sr, Ti, V, Nb, Mn, Ni, Cu, Pd, Zn, Hg, Sn, Pb) and SbF5in liquid aHF were investigated. Reactions with the MO (M?=?Mg, Ni, Cu and Zn) yielded H3OM(SbF6)3compounds. Both BeO and PdO didn't show any sign of reactivity meanwhile MO (M?=?V, Nb, Ti) gave products with M in oxidation state higher than two. The rest of the MO (M?=?Ca, Sr, Mn, Hg, Sn, Pb) formed mixtures of M(SbF6)2, H3OSbF6and/or H3OSb2F11. Reactions between H3OSbF6and M(SbF6)2(M?=?Fe, Co, Ni) also gave H3OM(SbF6)3compounds, meanwhile similar attempts with H3OSbF6and M(SbF6)2(M?=?Ca, Mn, Pd, Ag, Cd, Sn) to prepare [H3O]+/M2+/[SbF6]?salts failled. However, slow crystallizations of H3OSbF6and M(SbF6)2(M?=?Mn, Pd, Cd) mixtures resulted in the single crystal growth of new (H3O)3M(SbF6)5phases which crystal structures are not isotypic. Similar procedure with H3OSbF6/Cr(SbF6)2mixture resulted in few light orange crystals of (H3O)3[CrIV(SbF6)6](Sb2F11)·HF. Its crystal structure determination showed the presence of discrete [CrIV(SbF6)6]2?units where each of Cr atoms is found in a homoleptic coordination of six SbF6groups.
CATALYTIC FLUORINATION PROCESS OF MAKING HYDROHALOALKANE
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Paragraph 0071, (2013/05/23)
The present disclosure provides a fluorination process which involves reacting a hydrohaloalkene of the formula RfCCl=CH2 with HF in a reaction zone in the presence of a fluorination catalyst selected from the group consisting of TaF5 and TiF4 to produce a product mixture containing a hydrohaloalkane of the formula RfCFClCH3, wherein Rf is a perfluorinated alkyl group.
