7783-63-3Relevant articles and documents
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.
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.
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.
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
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.
