- Photochemical reaction channels of OCS with Cl2, ICI, or IBr isolated together in an argon matrix: Isolation of syn-iodocarbonylsulfenyl bromide
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The photolytically induced reactions of a dihalogen XY (= Cl2, ICl, or IBr) with OCS isolated together in an Ar matrix at about 15 K lead to different photoproducts depending on the natures of X and Y. In addition to the known species ClCO, OCCl2, syn-ClC(O)SCl, syn-ClC(O)SSCl, IC(O)Cl, IC(O)Br, and ^n-BrC(O)SBr, syn-iodocarbonylsulfenyl bromide, yyn-IC(O)SBr, has thus been identified for the first time as'a photoproduct of the reactions involving IBr. The first product to be formed in the reactions with Cl 2 or ICI is the C1CO radical which reacts subsequently with halogen or sulfur atoms or other matrix guests to give the corresponding carbonyl dihalide (OCCl2 and IC(O)Cl), syn-ClC(O)SCl or syn-ClC(O)SSCl. The analogous reaction with IBr affords syn-BrC(O)SBr, IC(O)Br, and syn-IC(O)SBr. The changes have been followed, the products characterized experimentally by IR measurements, and the spectra analyzed in the light of the results of appropriate theoretical calculations.
- Tobon, Yeny A.,Nieto, Laura I.,Romano, Rosana M.,Della Vedova, Carlos O.,Downs, Anthony J.
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- Formation of new halogenothiocarbonylsulfenyl halides, XC(S)SY, through photochemical matrix reactions starting from CS2 and a dihalogen molecule XY (XY = Cl2, Br2, or BrCl)
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Isolation of a dihalogen molecule XY (XY = Cl2, Br2, or BrCl) with CS2 in a solid Ar matrix at about 15 K leads, by broad-band UV-vis photolysis (200 ≤ λ ≤ 800 nm), to a variety of products depending on the natures of X and Y. These products have been identified on the basis of the IR spectra of the matrices. In addition to the familiar species SCCl2;, ClCS?, Cl ?...SCS, CCl4, ?CCl3, :CCl 2, SCl2, SCBr2, CBr4, ?CBr 3, BrC(S)Cl, BrCCl3, and :CBrCl, the following new molecules have also been identified as products of the various photoreactions: syn-CIC(S)SCI, anti-CIC(S)SCI, syn-BrC(S)SBr, anti-BrC(S)SBr, syn-ClC(S)SBr, anti-ClC(S)SBr, syn-BrC(S)SCl, anti-BrC(S)SCl, ClC(S)S?, BrCS?, and Br?...SCS. The IR spectra of these hitherto unknown species have been interpreted with reference to the predictions of ab initio (HF and MP2) and density functional theory (DFT) calculations. The results are analyzed in relation to the reaction pathways accessed by matrix photolysis.
- Tobon, Yeny A.,Romano, Rosana M.,Della Vedova, Carlos O.,Downs, Anthony J.
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- SPECTROSCOPIC AND KINETIC STUDIES OF THE SO RADICAL AND THE PHOTOLYSIS OF THIONYL CHLORIDE
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The primary processes occurring in the photolysis of SOCl//2 have been examined by use of kinetic absorption spectroscopy in the ultraviolet and vacuum ultraviolet. Photodissociation involves the fission of one sulfurchlorine bond, leaving an energized SOCl radical which may then undergo unimolecular decomposition to yield an SO radical and a further chlorine atom, or is stabilized by collision. The kinetics of the SO radical so formed are examined and a mechanism for removal is proposed. Two new electronic states of the SO radical are identified via new absorption systems in the vacuum ultraviolet.
- DONOVAN RJ,HUSAIN D,JACKSON PT
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- Synthesis of N,C bound sulfur, selenium, and tellurium heterocycles via the reaction of chalcogen halides with -CH3 substituted diazabutadiene ligands
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A series of N,C bound chalcogen heterocycles from the reaction of chalcogen halides (ChXn; Ch ) S, Se Te; X ) Cl, Br; n ) 2, 4) with N-alkyl or N-aryl 1,4-diazabutadiene (DAB) ligands featuring methyl substituents on the backbone C-C linkage ar
- Jason L. Dutton,Caleb D. Martin,Michael J. Sgro,Nathan D. Jones,Ragogna, Paul J.
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- VIBRATIONAL AND CHLORINE-35 NUCLEAR QUADRUPOLE RESONANCE SPECTRA OF SOME COMPLEXES OF ICl4(-) AND AuCl4(-). PART 1. TWO CRYSTAL MODIFICATIONS OF TRICHLOROSULPHONIUM TETRACHLOROIODATE,
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Two crystal modifications of have been characterised by elemental analysis, and Raman and n.q.r. spectroscopy.Analysis of the spectra indicates that both form I (stable) and form II (metastable) involve distortion from square planarity (D1h) of the ICl4(-) ions, a conclusion independently confirmed recently by an X-ray diffraction study of form I.On the basis of the Raman and n.q.r. spectra, the distortion in form II is similar to that observed in Na*2H2O.The origins of these distortions are discussed in terms of secondary bonding interactions in the solid state.
- Finch, Arthur,Gates, Peter N.,Page, Terence H.,Dillon, Keith B.,Waddington, Thomas C.
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- RuS4Cl12 and Ru2S6Cl16, two new ruthenium(II) complexes with SCl2 ligands
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Ru powder was reacted with SCl2 in closed silika ampoules at 140°C. From the black solution three compounds RuS4Cl12 1, Ru2S6Cl16 2, and Ru2S4Cl13 3 could be crystallized and characterized by x ray analysis. Black crystals of 1 (monoclinic, a = 9.853(1) A, b = 11.63(1) A, c = 15.495(1) A, β = 105.23(1)°, space group P21/c, z = 4) are identified as Trichlorsulfonium-tris(dichlorsulfan)trichlororuthenat(II) SCl3[RuCl3(SCl2)3]. In the structure the complex anions fac-[RuCl3(SCl2)3] and the cations [SCl3]+ are connected to ion pairs by three chlorine bridges. The brown crystals of 2 (triclinic, a = 7.754(2) A, b = 7.997(2) A, c = 10.708(2) A, α = 103.74(3)°, β = 98.44(3)°, γ = 108.58(3)°, space group P-1, z = 1) contain the binuclear complex Bis-μ-chloro-dichloro-hexakis(dichlorsulfan)-diruthenium(II), (SCl2)3ClRu(μ-Cl)2RuCl(SCl2) 3 with two fac-RuCl3(SCl2)3-units connected by two chlorine bridges. 3 was identifyed as a known mixed valence Ru(II,III) binuclear complex [Cl2(SCl2)Ru(μ-Cl)3Ru(SCl2) 3]. The vibrational spectra and the thermal behaviour of the compounds are discussed.
- Wagner, Christian,Herzog, Frank,Knaudt, Jutta,Thiele, Gerhard
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p. 279 - 284
(2008/10/08)
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- Bonding trends in (NSF)3 at high-pressures
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We report the results of a combined experimental and theoretical study into the high pressure behavior of crystalline trimerized thiazyl fluoride (NSF)3. The crystal exhibits a reversible pressure induced structural change at 80 kbar which is accompanied by a visible change in its color from translucent and yelowish at ambient pressure to black at high pressure. To explore the nature of bonding changes in this regime we performed semi-empirical SCF cluster calculations. Systematic examination of plausible intermolecular bonding configurations suggests that polymerization of the trimers into planar sheets or chains could account for the observed optical properties.
- Chizmeshya, A. V. G.,Coffman, P.,Robinson, S.,Petuskey, W. T.,Wolf, G. H.,McMillan, P. F.
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- Organic Heterocyclothiazenes. Part 13. Rotational Synthesis and Chemistry of 1,3,5,2,4-Trithiadiazines
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1,3,5,2,4-Trithiadiazines, previously formed from tetrasulphur tetranitride and diazoalkanes, are synthesised from 1,1-bis-sulphenyl chlorides (1; R = H, Cl), (5), (11) and bis(trimethylsilyl)sulphurdiimide (2), and this reaction extends to trithiadiazines with functional groups on carbon.Bis-sulphenyl chlorides (5a-d) are formed in one step from malonic esters and amides and sulphur dichloride.Pentathiepane (lenthionine) (14), prepared from di-iodomethane and disodium disulphide, gives methanebis(sulphenyl chloride) on chlorinolysis and hence, with (2), the parenttrithiadiazine (3; R = H).Similarly the pentathiepane (16) is converted into bis-sulphenyl chloride (11) and the spirotrithiadiazine (12).The sensitivity of the heterocyclic ring towards strongly polar reagents precluded the generation of the trithiadiazine cation (17) and anion (19), but the radical (18) is formed on treatment with benzoyl peroxide and benzoyl t-butyl nitroxide (22), resulting in the benzoyloxy and amino-oxy derivatives (21) and (24). m-Chloroperbenzoic acid or nitrogen tetroxide convert trithiadiazine into the S-oxide (25).
- Bannister, Robin M.,Rees, Charles W.
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p. 509 - 514
(2007/10/02)
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- Cyclic ethers which are substituted in a α-position by an isocyanide-dichloride group, and a process for their preparation
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The invention relates to new cyclic ethers which are substituted in the α-position by an isocyanide-dichloride group, of the formula STR1 in which R1, R2, R3, R4, R5 and n have the meaning indicated in the description, and to a process for their preparation.
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- On the Reactions of CF3SF4Cl, (CF3)2SF2, SF4, and OSCl2 with Trimethylsilyl Cyanide
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A moderately stable hexacoordinated sulfur(VI) compound with four different kinds of ligands, CF3SF2(CN)2Cl, results when CF3SF4Cl is reacted with (CH3)3SiCN.The latter compound also gives F2S(CN)2 and (CF3)2S(CN)2 with SF4 and (CF3)2SF2, respectively.These tetracoordinated sulfur(IV) compounds decompose rapidly at 25 deg C but are stable at lower temperatures.With OSCl2 and SCl2, the white solids OS(CN)2 and S(CN)2 result.This provides a new, convenient route to S(CN)2. - Keywords: (Trifluoromethyl)chlorodicyanodifluorosulfur(VI), Dicyanodifluorosulfur(IV), Dicyanobis(trifluormethyl)sulfur(IV), Thionyl Cyanide
- Kumar, Ramesh C.,Shreeve, Jean'ne M.
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p. 1407 - 1410
(2007/10/02)
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