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.
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).
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.
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.
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.