12597-33-0Relevant articles and documents
Theoretical and Experimental Studies of Six-Membered Selenium-Sulfur Nitrides SexS4-xN2 (x = 0-4). Preparation of S4N2 and SeS3N2 by the Reaction of Bis[bis(trimethylsilyl)amino]sulfane with Chalcogen Chlorides
Maaninen, Arto,Siivari, Jari,Suontamo, Reijo J.,Konu, Jari,Laitinen, Risto S.,Chivers, Tristram
, p. 2170 - 2177 (1997)
The reaction of [(Me3Si)2N]2S with equimolar amounts of SCl2 and S2Cl2 produces S4N2 in a good yield. The reaction of [(Me3Si)2N]2S with a 3:1:1 mixture of S2Cl2, Se2Cl2, and SeCl4 yields a dark brown-red insoluble material that was inferred to be mainly SSeSNSN on the basis of the elemental analysis, mass spectroscopy, vibrational analysis, and NMR spectroscopy. Attempts to prepare selenium-rich species resulted in the formation of elemental selenium or Se3N2Cl2. The experimental work was supported by ab initio MO calculations which establish the structural and stability relationships of the different members of the series 1,3-SexS4-xN2 (x = 0-4). Full geometry optimization was carried out for each molecular species using the polarized split-valence MIDI-4* basis sets. The effects of electron correlation were taken into account involving the second-order M?1er-Plessett perturbation theory. Each molecule was found to lie in an approximate half-chair conformation that is well established for 1,3-S4N2 (i.e., interacting planar NEN and EEE fragments; E = S, Se). The bond parameters agree well with experimental information where available. Whereas the lengths of the bonds in the NEEEN fragment approach those of the single bonds, the bonds in the NEN fragment show marked double bond character. The stabilities of the molecules decrease expectedly with increasing selenium content as judged by the total binding energy at the MP2 level of theory. Within a given chemical composition, isomers containing a N=Se=N unit lie higher in energy than those containing a N=S=N unit. These results may explain why selenium-rich SexS4-xN2 molecules have not been isolated.
Raman band of matrix isolated NaMSeN clusters
Herwig,Schnell,Becker
, p. 462 - 466 (2004)
Selenium clusters are doped with sodium atoms in the reaction zone of a dual laser vaporization source. Product clusters SeN and Na 2SeN with N=4-8 are deposited in a nitrogen matrix and investigated by Raman spectroscopy. Beside the Raman band of pure Se N clusters, a new intense band between 165 and 225 cm-1 is observed. Within a simple model of dynamical charge transfer the new band is attributed to certain vibrational modes with considerable changes of Na-Se bond lengths. The assignment is confirmed by density functional calculations. A bonding model for the Na2SeN clusters containing horseshoe shaped polyanionic selenium chains is developed.
Sandmeyer-Type Trifluoromethylthiolation and Trifluoromethylselenolation of (Hetero)Aromatic Amines Catalyzed by Copper
Matheis, Christian,Wagner, Victoria,Goossen, Lukas J.
supporting information, p. 79 - 82 (2016/01/25)
Aromatic and heteroaromatic diazonium salts were efficiently converted into the corresponding trifluoromethylthio- or selenoethers by reaction with Me4NSCF3 or Me4NSeCF3, respectively, in the presence of catalytic amounts of copper thiocyanate. These Sandmeyer-type reactions proceed within one hour at room temperature, are applicable to a wide range of functionalized molecules, and can optionally be combined with the diazotizations into one-pot protocols.
Syntheses of THF solutions of SeX2 (X = Cl, Br) and a new route to selenium sulfides SenS8-n (n = 1-5): X-ray Crystal Structures of SeCl2(tht)2 and SeCl2·tmtu
Maaninen, Arto,Chivers, Tristram,Parvez, Masood,Pietikaeinen, Jarkko,Laitinen, Risto S.
, p. 4093 - 4097 (2008/10/08)
A simple and efficient synthesis of solutions of pure SeCl2 in THF or dioxane (ca. 0.4 M) at 23 °C was achieved by treatment of elemental selenium with an equimolar amount of SO2Cl2. SeCl2 was characterized by 77Se NMR and Raman spectra. SeCl2 forms 1:1 or 1:2 adducts with tetramethylthiourea (tmtu) or tetrahydrothiophene (tht), respectively. The crystal structure of SeCl2·tmtu (1) reveals a T-shaped geometry [d(Se-Cl) = 2.443(4) A] with weak intramolecular Se-Cl interactions [d(Se-Cl) = 3.276(4) A]. Crystals of 1 are triclinic, space group P1, with a = 8.473(3) A, b = 9.236(3) A, c = 7.709(4) A, α = 109.90(3)°, β= 92.26(4)°, γ = 107.89(3)°, V = 532.9(4) A 3, and Z =2. The complex SeCl2(tht)2 (2) adopts a square planar geometry with d(Se-Cl) = 2.4149-(8) A. Crystals of 2 are monoclinic, space group C2/c, with a - 15.6784(8) A, b = 9.1678(4) A, c = 9.1246(4) A, β= 110.892(2)°, V = 1225.3(1) A,3 and Z = 4. The reaction of Ph3PS with SeCl2 gives Ph3PCl2 and a complex mixture of selenium Sulfides SenS8-n (n = 1-5), which were identified by 77Se NMR. Halogen exchange between SeCl2 and Me3SiBr in THF yields thermally unstable SeBr2 (ca. 0.4 M) characterized by 77Se NMR and Raman spectra.
