7784-35-2Relevant academic research and scientific papers
Organo-Uebergangsmetall-Chemie hochfluorierter Ligand-Systeme XIV. Vanadocenhexafluoroarsenat-Komplexe: Struktur von Cp2V(AsF6)2 und 51V-NMR von +-
Gowik, Petra,Klapoetke, Thomas M.,Siems, Karsten,Thewalt, Ulf
, p. 47 - 53 (1992)
The reaction behaviour of Cp2VCl2 towards the oxidizers AsF5, ClF3/AsF5, ClF, + - and WF6 has been investigated.Whereas in the reaction of Cp2VCl2 with AsF5 in the presence of NaF the vanadocene species is oxidized to yield +-, Cp2VCl2 does not react either with WF6 or with ClF or +- in dilute solution.Similarly, the vanadium in Cp2VCl2 is not oxidized by treatment with ClF3/AsF5 in CFCl3 solution but gives Cp2VCl(AsF6), +-, AsF3 and Cl2.The reaction of Cp2VCl2 with three equivalent of AsF3 affords Cp2V(AsF6)2, Cl2 and AsF3 in quantitative yield.In the presence of anhydrous HF Cp2VCl2 can be oxidized with either AsF5 or with AgAsF6 to give +-.The 51V NMR spectrum of +- has been recorded.The structure of Cp2V(AsF6)2 has been determined by a single crystal X-ray diffraction study.
Composition and Staging in the Graphite-AsF6 System and its Relationship to Graphite-AsF5
McCarron, Eugene M.,Bartlett, Neil
, p. 404 - 406 (1980)
Interconversion, of graphite-AsF5 intercalates and C12n+AsF6- salts, establishes the equilibrium: 3AsF5 + 2e- 2AsF6- + AsF3, for AsF5 intercalation, and simple staging-stoicheiometry relationships exist for
Unusual neutral ligand coordination to arsenic and antimony trifluoride
Levason, William,Light, Mark E.,Maheshwari, Seema,Reid, Gillian,Zhang, Wenjian
, p. 5291 - 5297 (2011/06/27)
The preparations and spectroscopic characterisation of the hydrolytically unstable As(iii) complexes, [AsF3(OPR3)2] (R = Me or Ph) and [AsF3{Me2P(O)CH2P(O)Me 2}] are described and represent the first examples of complexes of AsF3 with neutral ligands. The crystal structure of [AsF 3{Me2P(O)CH2P(O)Me2}] contains dimers with bridging diphosphine dioxide, but there are also long contacts between the dimers to neighbouring phosphine oxide groups, completing a very distorted six-coordination at arsenic and producing a weakly associated polymer structure. The reaction of AsF3 with OAsPh3 affords Ph3AsF2, and no arsine oxide complex was formed. Reaction of SbF3 with OER3 (R = Me or Ph, E = P or As), Me 2P(O)CH2P(O)Me2 and Ph2P(O)(CH 2)nP(O)Ph2 (n = 1 or 2) in MeOH produces [SbF3(OER3)2], [SbF3{Me 2P(O)CH2P(O)Me2}] and [SbF3{Ph 2P(O)(CH2)nP(O)Ph2}] respectively. The X-ray structures reveal that the complexes contain square pyramidal SbF 3O2 cores with apical F and cis disposed pnictogen oxides. However, whilst [SbF3(OER3)2] (R = Ph: E = P or As; R = Me: E = As) and [SbF3{Ph2P(O)CH 2P(O)Ph2}] are monomeric, [SbF3{Me 2P(O)CH2P(O)Me2}] is a dimer with bridging diphosphine dioxides producing a twelve-membered ring, and [SbF 3{Ph2P(O)(CH2)2P(O)Ph2}] is a chain polymer with diphosphine dioxide bridges. In the OAsR3 reactions with SbF3, R3AsF2 are also formed. Notably the Sb-O(P) bonds are shorter than As-O(P), despite the covalent radii (As 3. IR and multinuclear (1H, 19F and 31P) NMR data are reported and discussed. BiF3 does not react with pnictogen oxide ligands under similar conditions and halide exchange of bismuth chloro complexes with Me3SnF gave BiF3.
Preparations and properties of tris(perfluoroalkyl) arsenic and antimony(III, V) compounds
Naumann, Dieter,Nowicki, Gabriele,Sassen, Karl-Josef
, p. 1183 - 1189 (2008/10/09)
As(Rf)3 and Sb(Rf)3 (Rf = C2F5, C4F9, C6F13) are prepared in good yields by the polar reactions of AsCl3 and SbCl3/su
Preparation, structural and spectroscopic characterisation of the salts M3X3AF6 (A = As or Sb, M = S or Se, X = Cl or Br) containing the novel sulfur-and selenium-halogen cations (X2MMMX)+
Brownridge, Scott,Cameron, T. Stanley,Passmore, Jack,Schatte, Gabriele,Way, Todd C.
, p. 2553 - 2570 (2007/10/03)
The salts X2MMMX(AF6) (A = As or Sb, M = S or Se, X = Cl or Br) were prepared quantitatively by the reaction of stoichiometric amounts of MX3AF6 and M or from stoichiometric amounts of M, X2 and AsF5 (M = S or Se; X = Br) in liquid SO2. They have been characterised by elemental analysis, single-crystal X-ray diffraction, Fourier-transform (FT)-Raman and 77Se FT-NMR spectroscopy. The crystal structures of X2MMMX(AsF6) consist of (X2MMMX)+ cations and AsF6- anions. The structure of the (X2MMMX)+ cation is dominated by an intracationic halogen-chalcogen contact and M-M bond alternation giving rise to a short M-M bond distance indicative of thermodynamically stable npπ-npπ (n = 3 or 4) bonds. Since the structure of these cations is different from those of (YM)2MY+ (Y = Me or C6F5), theoretical calculations were performed to understand these differences and the bonding in these cations. In the X2SSSX(AsF6) salts (X = Cl or Br) the structures of the cations are disordered and therefore exact bond distances could be not obtained. However, bond distances were estimated from their FT-Raman spectra and supported by molecular orbital calculations. The FT-Raman spectrum of Se2Br5AsF6 is reported.
The Preparation and Characterization by Raman Spectroscopy of PI4+AsF6- containing the Tetraiodophosphonium Cation
Tornieporth-Oetting, Inis,Klapoetke, Thomas
, p. 132 - 133 (2007/10/02)
The thermodynamically unstable PI4+AsF6- containing the first and only example of a tetrahedral PI4+ cation, formally a derivative of the unknown PI5, was prepared by the reaction of PI3 and I3+AsF6- at low temperatures and characterized by Raman spectroscopy.
Synthesis and Characterization by Raman Spectroscopy of AsBr4AsF6; its Thermodynamic and Kinetic Stability and that of Related Salts
Klapoetke, Thomas,Passmore, Jack
, p. 3815 - 3822 (2007/10/02)
The thermodynamically and kinetically unstable salt AsBr4AsF6 was prepared by the reaction of stoicheiometric quantities of AsBr3, Br2, and AsF5, and characterized by Raman spectroscopy at -196 deg C.It was shown by Raman spectroscopy that AsBr4AsF6 decom
Organo-Uebergangsmetall-Chemie hochfluorierter Ligand-Systeme. X. Neue Organoniob(V)perfluoroborat-, arsenat-, und -antimonat-Komplexe
Gowik, Petra,Klapoetke, Thomas
, p. 35 - 44 (2007/10/02)
The quantitative oxidation of Cp2NbCl2 (Cp=η5-C5H5) with NO+, Ag+, I3+, AsF5 and F2 gives cationic niobium(V) derivatives of the type +>-> (X-=BF4-, AsF6-, SbF6-) in high yields.Reaction of with SbF5 and AgSbF6 gave and .The characterization was based on chemical analyses, NMR (1H, 19F), IR and mass spectral data; the structure of has been determined by X-ray diffraction.All oxidation reactions are discussed in terms of a simple thermodynamic model.
Preparation and solid-state and solution studies of three compounds of the tetraiodine dication I42+: I42+(AsF6-)2, I42+(SbF6-)2, and I42+(Sb3F14-)(SbF 6-)
Faggiani,Gillespie,Kapoor,Lock,Vekris
, p. 4350 - 4355 (2008/10/08)
Iodine is oxidized by AsF5 and SbF5 in solution in sulfur dioxide to give I4(AsF6)2 (1) and I4(Sb3F14)(SbF6) (2), respectively. I4(SbF6)2 (3) was prepared by the reaction of I2Sb2F11 with fluoride ion. Crystals of 1 are monoclinic, space group A2/m, with a = 5.876 (2) ?, b = 9.810 (4) ?, c = 12.411 (5) ?, β = 104.06 (4)°, V = 694.0 (4) ?3, and Dcalc = 4.17 g·cm-3 for Z = 2. Crystals of 2 are also monoclinic, space group P21/c, with a = 8.431 (2) ?, b = 15.968 (4) ?, c = 16.818 (3) ?, β = 100.48 (1)°, V = 2226.4 (8) ?3, and Dcalc = 4.10 g·cm-3 for Z = 4. Crystals of 3 are triclinic, space group P1, with a = 5.995 (1) ?, b = 10.054 (2) ?, c = 9.177 (2) ?, α = 122.85 (1)°, β = 119.08 (1)°, γ = 90.66 (1)°, V = 376.47 (14) ?3, and Dcalc = 4.32 g·cm-3 for Z = 1. The structures of 1 and 2 were solved by means of Patterson functions, and that of 3 was solved by direct methods. The three structures were refined by least squares to final agreement indices of R1 (R2) = 0.050 (0.059), 0.058 (0.062), and 0.066 (0.083) for 812, 3550, and 1316 independent reflections, respectively. 1 and 3 consist of discrete I42+ and AsF6- and SbF6- ions, respectively, and 2 consists of I42+, Sb3F14-, and SbF6- ions. The I42+ cation in all three compounds has a rectangular structure and may be considered to consist of two I2+ cations joined by two long weak bonds. Resonance Raman spectra were obtained from the solid compounds. The spectra had a single line at 232 cm-1 together with several overtones. In solution in SO2 and HSO3F at room temperature, the I42+ ion is dissociated to I2+, but at -78°C in HSO3F and SO2, I42+ is the predominant species.
The Preparation and Characterisation by Raman Spectroscopy of AsBr4+AsF6- containing the Tetrabromoarsenic (V) Cation
Klapoetke, Thomas,Passmore, Jack,Awere, Edward G.
, p. 1426 - 1427 (2007/10/02)
The thermodynamically unstable AsBr4+AsF6- was prepared by the reaction of AsBr3, Br2, and AsF5 at low temperatures, and characterised by Raman spectroscopy.
