7784-35-2Relevant articles and documents
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.
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.
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.
