CENTRO DE QUIMICA INORGANICA "DR. PEDRO J. AYMONINO"
Unidad Ejecutora - UE
Photochemical Reaction of OCSe with ClF in Argon Matrix: A Light-Driven Formation of XC(O)SeY (X, Y = F or Cl) Species
DELLA VÉDOVA, CARLOS O.; ROMANO, ROSANA M.; GÓMEZ CASTAÑO, JOVANNY A.; WILLNER, HELGE
JOURNAL OF PHYSICAL CHEMISTRY A
AMER CHEMICAL SOC
Lugar: Washington; Año: 2017 vol. 121 p. 2878 - 2878
The photochemistry of OCSe with ClF trapped together in argon matrices atcryogenic temperatures has been explored and the first interhalogen representatives of the elusive XC(O)SeY family, namely syn-ClC(O)SeF, anti-ClC(O)SeF, syn-FC(O)SeCl and anti-FC(O)SeCl, as well as the hitherto triatomic species ClSeF complexed by a CO molecule, were obtained. Both ClC(O)SeF conformers appear to be produced independently by photolysis of the respective precursors; while formation of both FC(O)SeCl structures is ruled by the presence of an angular molecular complex OCSe⋅⋅⋅Cl-F formed prior to photolysis. This latter photochemical pathway seems to favor the formation of the less stable anti-FC(O)SeCl structure instead of the more stable syn- one. With the aid of quantum chemical calculations, using ab-initio, DFT, TDDFT and CASSCF methods, the mechanism for this photochemical reaction is rationalizedboth in terms of radical processes as well as a photo-induced electron transfer occurring into the OCSe⋅⋅⋅Cl-F complex. Also a singlet-triplet conical intersection between anti and syn rotamers of the FC(O)SeCl molecule is theoretically explored.