Photochemical Reaction Channels of OCS with Cl2, ICl or IBr Isolated Together in an Argon Matrix: Isolation of syn-IC(O)SBr

YENY A. TOBÓN; LAURA I. NIETO; ROSANA M. ROMANO; CARLOS O. DELLA VÉDOVA; ANTHONY J. DOWNS

Journal of Physical Chemistry A

Año: 2006 vol. 110 p. 2674 - 2681

1089-5639

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 syn-BrC(O)SBr, syn-iodocarbonylsulfenyl bromide, syn-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 Cl2 or ICl is the ClCO 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.) 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 syn-BrC(O)SBr, syn-iodocarbonylsulfenyl bromide, syn-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 Cl2 or ICl is the ClCO 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.