Formation of New Halogenothiocarbonylsulfenyl Halides, XC(S)SY, through Photochemical Matrix Reactions Starting from CS2 and a Dihalogen Molecule XY (XY = Cl2, Br2, or
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- 作者：Yeny A. Tobó ; n ; Rosana M. Romano ; Carlos O. Della Vé ; dova ; Anthony J. Downs
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：May 28, 2007
- 年：2007
- 卷：46
- 期：11
- 页码：4692 - 4703
- 全文大小：230K
- 年卷期：v.46,no.11(May 28, 2007)
- ISSN：1520-510X
文摘
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 
800 nm), to a variety of products depending on the natures of X andY. These products have been identified on the basis of the IR spectra of the matrices. In addition to the familiarspecies SCCl2, ClCS
, Cl···SCS, CCl4, CCl3, :CCl2, SCl2, SCBr2, CBr4, CBr3, BrC(S)Cl, BrCCl3, and :CBrCl, thefollowing new molecules have also been identified as products of the various photoreactions: syn-ClC(S)SCl,anti-ClC(S)SCl, 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 withreference to the predictions of ab initio (HF and MP2) and density functional theory (DFT) calculations. The resultsare analyzed in relation to the reaction pathways accessed by matrix photolysis.
800 nm), to a variety of products depending on the natures of X andY. These products have been identified on the basis of the IR spectra of the matrices. In addition to the familiarspecies SCCl2, ClCS, Cl···SCS, CCl4, CCl3, :CCl2, SCl2, SCBr2, CBr4, CBr3, BrC(S)Cl, BrCCl3, and :CBrCl, thefollowing new molecules have also been identified as products of the various photoreactions: syn-ClC(S)SCl,anti-ClC(S)SCl, 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 withreference to the predictions of ab initio (HF and MP2) and density functional theory (DFT) calculations. The resultsare analyzed in relation to the reaction pathways accessed by matrix photolysis.