7783-70-2Relevant articles and documents
Solid-State Structure of Protonated Ketones and Aldehydes
Stuart, Daniel,Wetmore, Stacey D.,Gerken, Michael
, p. 16380 - 16384 (2017)
Protonated carbonyl compounds have been invoked as intermediates in many acid-catalyzed organic reactions. To gain key structural and electronic data about such intermediates, oxonium salts derived from five representative examples of ketones and aldehydes are synthesized in the solid state, and characterized by X-ray crystallography and Raman spectroscopy for the first time. DFT calculations were carried out on the cations in the gas phase. Whereas an equimolar reaction of the carbonyl compounds, acetone, cyclopentanone, adamantanone, and acetaldehyde, with SbF5 in anhydrous HF yielded mononuclear oxonium cations, the same stoichiometry in a reaction with benzaldehyde resulted in formation of a hemiprotonated, hydrogen-bridged dimeric cation. Hemiprotonated acetaldehyde was obtained when a 2:1 ratio of aldehyde and SbF5 was used. Experimental and NBO analyses quantify the significant increase in electrophilicity of the oxonium cations compared to that of the parent ketones/aldehydes.
Hexakis(carbonyl)iron(II) undecafluorodiantimonate(V), [Fe(CO)6][Sb2F11]2, and -hexafluoroantimonate(V), [Fe(CO)6][SbF6]2, their syntheses, and spectroscopic and structural characterization by single crystal X-ray diffraction and normal coordinate analysis
Bernhardt, Eduard,Bley, Bianca,Wartchow, Rudolf,Willner, Helge,Bill, Eckhard,Kuhn, Peter,Sham, Iona H. T.,Bodenbinder, Matthias,Br?chler, Raimund,Aubke, Friedhelm
, p. 7188 - 7200 (1999)
Hexakis(carbonyl)iron(II) undecafluorodiantimonate(V), [Fe(CO)6][Sb2F11]2, is conveniently prepared by the oxidative carbonylation of Fe(CO)5 with XeF2 as external oxidizer in the conjugate Bronsted-Lewis superacid HF-SbF5. The colorless compound crystallizes from the reaction medium in high purity. The molecular structure is obtained by single-crystal X-ray diffraction. The cation is a regular octahedron, while the vertex-shared di-octahedral [Sb2F11]- anion is distorted from D4(h) symmetry by bending and rotational processes, due to significant interionic interactions, primarily of the F · · · C type. Washing of [Fe(CO)6][Sb2F11]2 with anhydrous HF results in an unusual elution of SbF5 and the quantitative conversion to hexakis(carbonyl)iron(II) hexafluoroantimonate(V) [Fe(CO)6][SbF6]2. The molecular structure of the salt shows octahedral ions with slight tetragonal distortions for the cation (elongation) and the anion (compression). Both salts are thermally stable up to 150 °C. The averaged bond distances and the vibrational wavenumbers of [Fe(CO)6]2+ are nearly identical in both compounds. The [Fe(CO)6]2+ cation, the first and so far only isolated and structurally characterized dipositive, superelectrophilic carbonyl cation formed by a 3d-metal, is further characterized by a normal coordinate analysis (NCA). The obtained force constants are compared to those of the isoelectronic molecule Cr(CO)6. Changes in π-back-bonding affect the F(CO/CO) and F(CO/MC) interaction force constants more strongly than the stretching force constants F(CO) and F(MC). All 13 fundamentals of [Fe(CO)6]2+ are detected and assigned with the help of the data obtained from the normal coordinate analysis and density functional calculations published previously. The electronic ground state 1A1(g) of the [Fe(CO)6]2+ cation is established by magnetic susceptibility measurements of polycrystalline [Fe(CO)6][SbF6]2 and [Fe(CO)6][Sb2F11]2 between 2 and 300 K. The magnetic impurity formed during synthesis is identified as Fe[SbF6]2 which has iron(II) in high spin (5T2(g)) ground state. Consistent with a diamagnetic ground state are the single line in the 57Fe Mossbauer spectrum (i.s. = -0.003(8) mm s-1 relative to α-Fe), obtained on polycrystalline samples and the single sharp line in the 13C NMR spectrum in DF solution at 178 ppm with J (57Fe- 13C) of 19.2 Hz.
Preparation and characterization of (CNSSS)2(A)2 (A = AsF6-, SbF6-, Sb2F 11-) containing the O2-like 5,5′-Bis(1,2,3,4-trithiazolium) dication: The second example of a simple nonsterically hindered main-group diradical that retains its paramagnetism in the solid state
Cameron, T. Stanley,Decken, Andreas,Grein, Friedrich,Knapp, Carsten,Passmore, Jack,Rautiainen, J. Mikko,Shuvaev, Konstantin V.,Thompson, Robert C.,Wood, Dale J.
, p. 7861 - 7879 (2010)
The reaction of NC-CN with a 1:1 mixture of S4(MF 6)2 and S8(MF6)2 (M = As, Sb) (stoichiometrically equivalent to four S3MF 6 units) results in the quantitative formation of S 3NCCNS3(MF6)2 [7(MF 6)2], which is the thermodynamic sink in this reaction. The Sb2F11- salt 7(Sb2F 11)2 is prepared by the addition of an excess of SbF 5 to 7(AsF6)2. Crystal structure determinations for all three salts show that 72+ can be viewed as two R-CNS 3+ radical cations joined together by a C-C single bond. The two rings are coplanar and in a trans orientation due to electrostatic Nδ-...Sδ+ interactions. The classically bonded alternative (quinoidal structure), in which the octet rule is obeyed, is not observed and is much higher in energy based on calculated estimates and a simple comparison of π bond energies. Calculated molecular orbitals (MOs) support this, showing that the MO corresponding to the quinoidal structure lies higher in energy than the nearly degenerate singly occupied MOs of 7 2+. The vibrational spectra of 72+ in all salts were assigned based on a normal-coordinate analysis and theoretical vibrational frequencies calculated at the PBE0/6-31G* level. In the solid state, 72+ is a planar disjoint diradical with essentially degenerate open-shell singlet and triplet states. The disjoint nature of the diradical cation 72+ is established by magnetic susceptibility studies of the Sb2F11- salt doped in an isomorphous diamagnetic host material (CNSNS)2(Sb2F11) 2 [10(Sb2F11)2]. Intramolecular spin coupling is extremely weak corresponding to a singlet-triplet gap (δEST = 2J) of -1. CASPT2[12,12]/6-311G* calculations support a triplet ground state with a small singlet-triplet gap. The single-crystal electron paramagnetic resonance (EPR) of 7(Sb2F11)2 doped in 10(Sb 2F11)2 is in agreement with the triplet state arising from the weak coupling between the unpaired electrons residing in p π orbitals in each of the rings. Variable-temperature susceptibility data for bulk samples of 7(A)2 (A = SbF 6-, AsF6-, Sb2F 11-) are analyzed by employing both 1D chain and 2D sheet magnetic models. These studies reveal significant intermolecular exchange approximating that of a 1D chain for the SbF6- salt with |J| = 32 cm-1. The exchange coupling is on the same order of magnitude as that for the AsF6- salt, although in this case it is likely that there are complex exchange pathways where no particular one is dominant. Intermolecular exchange in the Sb2F 11- salt is an order of magnitude weaker. In solution, the EPR spectrum of 72+ shows a broad triplet resonance as well as a sharp resonance that is tentatively attributed to a rotomer of the 7 2+/anion pair, which is likely the origin of the green species given on dissolution of the red 72+ salts in SO2/AsF 3/MF5. We account for the many similarities between O 2 and 72+, which are the only simple nonsterically hindered nonmetal diradicals to retain their paramagnetism in the solid state. 72+ is also the first isolable, essentially sulfur-based diradical as evidenced by calculated spin densities.
Mixed Noble-Gas Compounds of Krypton(II) and Xenon(VI); [F5Xe(FKrF)AsF6] and [F5Xe(FKrF)2AsF6]
Lozin?ek, Matic,Mercier, Hélène P. A.,Schrobilgen, Gary J.
, p. 8149 - 8156 (2021)
The coordination chemistry of KrF2 has been limited in contrast with that of XeF2, which exhibits a far richer coordination chemistry with main-group and transition-metal cations. In the present work, reactions of [XeF5][AsF6] with KrF2 in anhydrous HF solvent afforded [F5Xe(FKrF)AsF6] and [F5Xe(FKrF)2AsF6], the first mixed krypton/xenon compounds. X-ray crystal structures and Raman spectra show the KrF2 ligands and [AsF6]? anions are F-coordinated to the xenon atoms of the [XeF5]+ cations. Quantum-chemical calculations are consistent with essentially noncovalent ligand?xenon bonds that may be described in terms of σ-hole bonding. These complexes significantly extend the XeF2–KrF2 analogy and the limited chemistry of krypton by introducing a new class of coordination compound in which KrF2 functions as a ligand that coordinates to xenon(VI). The HF solvates, [F5Xe(FH)AsF6] and [F5Xe(FH)SbF6], are also characterized in this study and they provide rare examples of HF coordinated to xenon(VI).
Fluoride Ion Donor Properties of UF2O2; Preparation and Characterization of the Adducts UF2O2*nSbF5 (n=2 or 3) and Crystal Structure of UF2O2*3SbF5
Fawcett, John,Holloway, John H.,Laycock, David,Russell, David R.
, p. 1355 - 1360 (1982)
The adducts UF2O2*nSbF5 (n=2 or 3) have been obtained as pale green and pale yellow-green solids respectively from the reaction of UF2O2 with SbF5 in HF solvent.The solid adducts have been characterized by observation of reaction stoicheiometries, chemical analyses, and vibrational spectra.An X-ray diffraction study has shown that crystals of UF2O2*3SbF5 are monoclinic, space group P21/n, with unit-cell dimensions a=11.040(7), b=12.438(12), c=12.147(8) Angstroem, β=111.16(20) degree, and Z=4.The structure has been refined by three-dimensional least-squares methods to R=0.0773 for 1613 reflections.The structure is best regarded as a fluorine-bridged network of UF2O2 and SbF5 molecules in which the antimony is surrounded by a distorted octahedron of fluorine atoms and the uranium by a pentagonal-bipyramidal array of five fluorines and two oxygens.Two of the uranium-fluorine distances are long and this means that the structure can also be described in terms of zigzag chains of UO2 groups fluorine-bridged to SbF6 units with Sb2F11 side-chains attached to the uraniums.
Trifluoroacetate as a Bridging Ligand for Antimony(V): Crystal and Molecular Structures of μ-Fluoro-μ-trifluoroacetato-bis (1) and of μ-Oxo-di-μ-trifluoroacetato-bis (2)
Bullivant, David P.,Dove, Michael F. A.,Haley, Martin J.
, p. 109 - 114 (1980)
Crystals of title compound (1), Sb2(O2CCF3)F9, are monoclinic.Space group P21/c with a=9.386(6), b=15.119(8), c=16.250(7) Angstroem, β=110.52(11) deg, and Z=8.The asymmetric unit contains two equivalent but crystallographically independent binuclear complexes in which the Sb atoms are bridged by a F atom (Fb) and by a trifluoroacetato-group.The distorted octahedral co-ordination at each Sb centre is completed by four terminal F atoms (Ft).The mean bond distances are: Sb-Fb 2.025(21), Sb-O 2.026(23), and Sb-Ft 1.836(24) Angstroem.The heavy atoms have been located directly and full-matrix least-squares refinement with anisotropic thermal parameters for the Sb atoms has given R=0.090 with 1 791 independent observed reflections.Title compound (2), Sb2O(O2CCF3)2F6, crystallizes in the monoclinic space group Cc with a=12.322(6), b=13.867(8), c=9.443(5) Angstroem, β=122.75(5) deg, and Z=4.The two Sb atoms are bridged by an oxygen atom (Ob) and by two trifluoroacetato-groups with the octahedral co-ordination at Sb completed by terminal fluorines (Ft).The binuclear complex has approximate C2v symmetry and exhibits the following mean bond distances: Sb-Ob 1.893(21), Sb-O 2.064(16), and Sb-Ft 1.840(17) Angstroem.The analysis is based on 1 760 independent observed reflections and refined by weighted full-matrix least-squares analysis to R=0.043.
Crystal Structures of Hydrazinium(II) Salts of [SbF6]- and [Sb2F11]-
Mazej, Zoran,Goreshnik, Evgeny A.
, p. 1216 - 1219 (2015)
N2H6(Sb2F11)2 was synthesized by the reaction of N2H6F2 with excess of SbF5 in anhydrous hydrogen fluoride (aHF). It crystallizes in the triclinic space group P 1ˉ (No. 2) with a = 6.6467(3) ?, b = 8.3039(4) ?, c = 8.3600(5) ?, α = 76.394(5) o, β = 70.161(5) o, γ = 70.797(5) o, V = 405.90(4) ?3 at 150 K, Z = 2. When it is redissolved in aHF, it solvolysis with the release of SbF5 yielding N2H6(SbF6)2 which crystallizes in the monoclinic C2/c space group (No. 15) with a = 7.3805(3) ?, b = 12.3248(5) ?, c = 10.4992(4) ?, β = 92.218(4) o, V = 954.33(7) ?3 at 150 K, and Z = 8. No other phases were observed in crystallization products when different molar ratios of N2H6F2/SbF5 (1:1,2:3,1:3) in aHF were used as starting materials.
METHOD FOR MANUFACTURE OF 1,1,1-TRIFLUORO-2-CHLOROETHANE (HCFC 133A) AND/OR TRFLUOROETHYLAMINE (TFEA)
-
Page/Page column 26, (2020/06/05)
A method for manufacture of 1, 1, 1-trifluoro-2-chloroethane (HCFC-133a) and/or trifluoroethylamine (TFEA), wherein at least one reaction step takes place in a microreactor that is comprising or is made of SiC-microreactor, the processes can be efficiently combined in that HCFC-133a produced by using a microreactor, may preferably advantageously serve as starting material and/or intermediate material in the manufacture of TFEA. The HCFC-133a and/or the TFEA can be easily, by a method with only low energy consumption, purified and/or isolated, and preferably the process for purifying and/or isolating does not require a distillation. Advantageously, the separation from excess hydrogen fluoride (HF) and catalyst can easily take place in an energy-saving manner by phase separation.
Reactions of antimony compounds with fluorine gas by thermogravimetric and differential thermal analyses and X-ray diffraction analysis
Watanabe, Daisuke,Akiyama, Daisuke,Sato, Nobuaki
, p. 1 - 7 (2018/08/06)
Antimony is one of the key fission products in the reprocessing of spent nuclear fuel by the fluoride volatility method because of the high volatility of antimony fluorides. Since the fluorination reaction of antimony compounds is not well understood, the reaction behavior of antimony compounds with F2 was investigated by thermogravimetric and differential thermal analyses and X-ray diffraction analysis in this study. The target antimony compounds were antimony metal, SbF3, Sb2O3, Sb2O4, and Sb2O5. The fluorination reaction of antimony metal started at 150 °C, and the fluorination product was SbF3. SbF3 volatilized completely by the reaction with F2 above 190 °C; it was considered that volatile SbF5 was formed by the reaction with F2. In the series of fluorination of the antimony oxides, Sb2O3, Sb2O4, and Sb2O5, they started to react with F2 and volatilize at 330 °C as SbF5. During the fluorination of Sb2O3, Sb2O4 was formed temporarily in the course of the reaction. Oxygen released from the fluorination reaction of a part of Sb2O3 would oxidize remained Sb2O3 to Sb2O4. The reaction mechanism for the fluorination of antimony compounds obtained in this study is applicable to evaluate the transfer of antimony in the reprocessing process of the fluoride volatility method.
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.
