12512-13-9Relevant articles and documents
Concentrations of Isomers of Type PmAs4-mX3 in P4S3-As4S3 and P4Se3-As4Se3 Mixtures
Baldus, Hans P.,Blachnik, Roger,Schneider, Claudia
, p. 515 - 524 (1988)
The reactions of P4S3 with As4S3 and of P4Se3 with As4Se4 in the molten state yields molecules of the type PmAs4-mS3 and PmAs4-mSe3, respectively.A method was developed to separate the different components by the HPLC technique, and to determine their concentrations.The identification of the isomers in the HPLC pattern was achieved with the aid of the LC-MS method.In the selenium system, the distribution of the different species is statistical.In the system P4S3-As4S3, the formation of PAs3S3 with one phosphorus atom in the apical position is favoured. - Keywords: HPLC study of P4S3-As4S3 and P4Se3-As4Se3 mixtures; Constitution isomers of phosphorus arsenic chalcogenides; Equilibrium constants of phosphorus-arsenic exchange reactions
Homoleptic Silver Complexes of the Cages P4Se3 and As4S3
Weis, Philippe,Hettich, Clarissa,Kratzert, Daniel,Krossing, Ingo
, p. 1657 - 1668 (2019)
By reacting P4Se3 and As4S3 with Ag[Al(ORF)4] {–RF = –C(CF3)3 or –hfip [= –C(H)(CF3)2]} in suitable solvents, Ag(P4Se3)[Al(Ohfip)4] (1), Ag(P4Se3)2[Al(ORF)4] (2), Ag(P4Se3)3[Al(ORF)4] (3), Ag2(As4S3)3[Al(ORF)4]2 (4) and Ag(As4S3)2[Al(ORF)4] (5) were synthesized and characterized by SC-XRD, Mass spectrometry, Raman spectroscopy as well as solution NMR spectroscopy. When using stronger coordinating anions, only P4Se3 forms an isolable complex yielding 1 featuring a [Ag2(P4Se3)2]2+ core capped by anions acting as the first example of P4Se3 coordinating through selenium atoms. Upon using the weakly coordinating anion [Al{OC(CF3)3}4]–, the dimeric complexes 2 and 4 are accessible in dichloromethane or ortho-difluorobenzene (o-dfb), respectively. Complex 2 shows isolated [Ag2(P4Se3)4(CH2Cl2)2]2+ dications with a [Ag2(P4Se3)2]2+ core similar to 1. Complex 4 shows isolated [Ag2(As4S3)3]2+ dications featuring a weak argentophilic contact. All of these complexes include solvent molecules or anions in the coordination sphere of the metal. When switching to the polar yet non-coordinating solvent SO2, the coordination spheres are filled with additional ligands and compounds 3 and 5 form. Complex 3 shows condensed [Ag(P4Se3)3]+ units yielding a one dimensional chain and represents the first homoleptic metal(P4Se3) complex. Complex 5 shows a similar paddle wheel structure as in 4 with interconnecting As4S3 ligands and is the first known example of a homoleptic metal(As4S3) complex.
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.
