12279-90-2Relevant articles and documents
Neue FeAsS-Kaefigstrukturen aus +Fe(CO)2>2 (Cp+ = C5Me4Et) und Realgar
Brunner, Henri,Poll, Ludwig,Wachter, Joachim,Nuber, Bernhard
, p. 117 - 122 (1994)
The reaction of +Fe(CO)2>2 (Cp+ = η5-C5Me4Et) with equimolar amounts of As4S4 in boiling toluene gives Cp+2Fe2As2S2 (1) and Cp+2Fe2As2S3 (2).Both complexes form with two equivalents of Cr(CO)5THF the bisadducts Cp+2Fe2As2S2*2Cr(CO)5 (3) and Cp+2Fe2As2S3*2Cr(CO)5 (4), respectively.The Cr(CO)5 fragments are bound to the As atoms.X-ray diffraction analyses have been carried out for 1 and 4.The structure of 1 contains two coplanar η2-AsS bridges which bisect the Fe-Fe vector and are parallel to the Cp+ ligands.Complex 1 is formulated as a 30e tripledecker complex for it contains an As-As distance (2.629(1) Angstroem) very close to As-As bonding.The structure of 4 contains a Fe2As2S3 cage.The inorganic ligand is formally built up by two syn oriented AsS units which are bridged by a S atom.Such a view is supported by the conversion of 1 into 2 by reaction with a mild sulfur donator, e.g.As4S4.Key words: Chromium; Iron; Carbonyl; Arsenic, Sulfur; Cage compound
The reaction of as4Sn (n = 3, 4) and as2S3 with (C5Me4R)2Co2(CO)2 (R = Me, Et): Fragmentation and of by organometallic complexes
Brunner, Henri,Kauermann, Heike,Poll, Ludwig,Nuber, Bernhard,Wachter, Joachim
, p. 657 - 662 (1996)
The reaction of Cp2#Co2(CO)2 1 (Cp# = Cp* or Cpx; Cp* = C5Me5: a; Cpx = C5Me4Et: b) with equimolar amounts of As4Sn (n = 3, 4) and As2S3 was investigated at different temperatures. The formation of Cp2#Co2(CO)As2S2 3, Cp2#Co2As2S3 4, Cp3#Co3As2S4 5, and Cp3#Co3As4S2 6 was observed in ratios depending on the reaction conditions. Starting from As4S4 or As4S3 and 1b insertion of a CpxCo(CO) fragment into one of the As-As bonds of the cages was achieved in low yields leading to CpxCo(CO)As4S4 2b and CpxCo(CO)As4S3 8, respectively. Structures were studied by means of IR and 1H-NMR spectroscopy and X-ray diffraction analyses. Cp2#Co2{CO}As2S2 3 may be supposed to be the key intermediate in the whole reaction sequence: On heating solutions of 3 complexes 4-6 of higher nuclearity and different connectivity within the inorganic ligand were formed. VCH Verlagsgesellschaft mbH, 1996.
(HgBr2)3(As4S4)2: An adduct of HgBr2 molecules and undistorted as4S 4 cages
Braeu, Michael F.,Pfitzner, Arno
, p. 935 - 937 (2007)
(HgBr2)3(As4S4)2 is obtained by high temperature reaction of stoichiometric amounts of HgBr 2 and As4S4. It crystallizes in the monoclinic space group P21/c with the lattice constants a = 9.593(5) A, b = 11.395(5) A, c = 13.402(5) A, β= 107.27(3)°, V = 1399(1) A3, and Z = 2. The crystal structure consists of molecular units built from two undistorted As4S4 cages which are coordinated weakly by three almost linear HgBr2 units. Raman spectra clearly indicate minor bonding interactions between HgBr2 and As 4S4.
Regularities of the Interaction of Copper, Cobalt, and Iron Arsenides with Sulfur under Nonequilibrium Conditions
Isabaev,Kuzgibekova,Chunaeva
, p. 1952 - 1953 (2008/10/08)
The regularities in the sulfiding of arsenides of copper, cobalt, and iron by elemental sulfur under nonequilibrium conditions are studied by the physicochemical methods of analysis. The temperature intervals of the interaction, the phases of the intermediate stages, and the role of heterogeneous reactions in the sulfide-formation mechanism are determined.
Preparation, X-ray crystal structures, and vibrational spectra of some salts of the As3S4+ and As3Se4+ cations
Christian, Beverley H.,Gillespie, Ronald J.,Sawyer, Jeffery F.
, p. 3410 - 3420 (2008/10/08)
The reactions of α- and β-As4S4 and some arsenic-selenium melts with various oxidants in SO2 as solvent are reported. It is shown by X-ray crystallography that the reactions of As4S4 and a 1:1 As-Se melt with the Lewis acids AsF5 and SbF5 in a 1:3 molar ratio in SO2 give the hexafluoroarsenate and hexafluoroantimonate salts of the novel arsenic chalcogen cations As3S4+ and As3Se4+. Crystals of (As3S4)(SbF6) are yellow plates which crystallize in the orthorhombic space group Pcam with a = 20.453 (4) A?, b = 5.990 (1) A?, c = 9.609 (2) A?, U = 1177.3 (4) A?3, and dc = 3.32 g cm-3 for Z = 4. Crystals of the isomorphous (As3S4)(AsF6) are dark yellow prisms and rhombs with cell dimensions a = 19.962 (4) A?, b = 5.930 (1) A?, c - 9.441 (3) A?, U = 1115.8 (5) A?3, and dc = 3.22 g cm-3 for Z = 4. The compound (As3Se4)(SbF6) forms orange diamond-shaped plates which crystallize in the monoclinic space group P21/m with a = 6.224 (3) A?, b = 9.564 (5) A?, c = 10.643 (5) A?, β = 92.65 (4)°, U = 632.9 (5) A?3, and dc = 4.07 g cm-3 for Z = 2. The structure of the compound (As3S4)(SbF6) was solved by using the Patterson function and refined by least-squares methods to final agreement indices R1 = 0.036 and R2 = 0.043 for 699 observed data. The isomorphous compound (As3S4)(AsF6) has similarly been refined by least-squares methods to final agreement indices R1 = 0.043 and R2 = 0.052 for 546 observed data. The structure of the compound (As3Se4)(SbF6) was solved by using direct methods and has been refined by least-squares to final agreement indices R1 = 0.064 and R2 = 0.082 for 620 observed reflections. The two cations As3S4+ and As3Se4+ are isostructural with crystallographic mirror symmetry and an overall symmetry of Cs. The cage structure of the two cations can be derived by bridging three edges of a tetrahedron of three arsenic and one sulfur or selenium atoms by the remaining sulfur or selenium atoms. Bond distances, bond angles and some significant interionic contact distances in these compounds are discussed. In addition, the Raman and IR spectra of these cations as well as the Raman spectrum of As4S3 and an improved Raman spectrum of the compound α-As4S4 are reported.
