CEQUINOR (UNLP-CONICET), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 esq. 115, (1900) La Plata, Argentina.
Phys Chem Chem Phys. 2010 Jan 21;12(3):563-71. doi: 10.1039/b914862k. Epub 2009 Nov 12.
Molecular complexes between OCS and ClF, Cl(2), Br(2), or BrCl have for the first time been isolated in solid matrixes at low temperature, and characterized by their IR spectra. 1 : 1 adducts between OCS and ClF, Cl(2), or BrCl were formed by broad-band UV-visible photolysis of matrix-isolated FC(O)SCl, ClC(O)SCl or BrC(O)SCl, respectively. Co-deposition of gaseous mixtures of OCS and ClF or Br(2) diluted with Ar on a CsI window cooled to approximately 15 K led to the identification of 1 : 1 complexes, while similar mixtures of OCS and Cl(2) gave rise mainly to 1 : 2 species. The differences in the structures and stoichiometries of the molecular complexes may well be responsible for the different reaction channels observed for the photochemical matrix reactions between OCS and Cl(2) or Br(2). The structures, energy differences, vibrational spectra, and bonding properties of all the possible complexes formed between OCS and XY (XY = ClF, Cl(2), Br(2), or BrCl) have been studied with different theoretical approximations.
OCS 与 ClF、Cl(2)、Br(2)或 BrCl 的分子复合物首次在低温下被分离出来，并通过其红外光谱进行了表征。通过对 FC(O)SCl、ClC(O)SCl 或 BrC(O)SCl 的基质隔离宽带紫外可见光解，分别形成了 OCS 与 ClF、Cl(2)或 BrCl 的 1:1 加合物。将 OCS 和 ClF 或 Br(2)的混合气体与 Ar 一起在 CsI 窗上共沉积，冷却至约 15 K，可鉴定出 1:1 复合物，而 OCS 和 Cl(2)的类似混合物主要生成 1:2 物种。分子复合物的结构和化学计量的差异很可能是导致 OCS 与 Cl(2)或 Br(2)之间光化学反应的不同反应通道的原因。用不同的理论近似方法研究了 OCS 与 XY（XY = ClF、Cl(2)、Br(2)或 BrCl）之间可能形成的所有复合物的结构、能量差异、振动光谱和键合性质。
