Department of Chemistry, State Key Laboratory of Advanced Textiles Materials and Manufacture Technology of the Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, China.
J Phys Chem A. 2013 Jul 11;117(27):5664-74. doi: 10.1021/jp4032095. Epub 2013 Jul 1.
Reactions of the ground-state titanium and zirconium monoxide and dioxide molecules with monochloromethane in excess argon matrixes have been investigated in solid argon by infrared absorption spectroscopy and density functional theoretical calculations. The results show that the ground-state MOx (M = Ti, Zr; x = 1, 2) molecules react with CH3Cl to first form the weakly bound MO(CH3Cl) and MO2(CH3Cl) complexes. The MO(CH3Cl) complexes can rearrange to the CH3M(O)Cl isomers with the Cl atom of CH3Cl coordination to the metal center of MO upon UV light irradiation (λ < 300 nm). Theoretical calculations indicate that the electronic state crossings exist from the MO + CH3Cl reaction to the more stable CH3M(O)Cl molecules via the MO(CH3Cl) complexes traversing their corresponding transition states. The MO2(CH3Cl) complexes can isomerize to the more stable CH3OM(O)Cl molecules with the addition of the C-Cl bond of CH3Cl to one of the O═M bonds of MO2 upon annealing after broad-band light irradiation. The C-Cl activation by the MOx mechanism was interpreted by the calculated potential energy profiles.
在固体氩气中，通过红外吸收光谱和密度泛函理论计算，研究了过量氩基质中基态钛和锆的一氧化物和二氧化物分子与一氯甲烷的反应。结果表明，基态 MOx（M = Ti，Zr；x = 1，2）分子与 CH3Cl 反应，首先形成弱束缚的 MO（CH3Cl）和 MO2（CH3Cl）配合物。在紫外光照射下（λ < 300nm），MO（CH3Cl）配合物可以通过 CH3Cl 的 Cl 原子与 MO 的金属中心配位，重排为 CH3M（O）Cl 异构体。理论计算表明，通过 MO（CH3Cl）配合物穿越相应的过渡态，从 MO + CH3Cl 反应到更稳定的 CH3M（O）Cl 分子，存在电子态交叉。在宽带光照射后退火时，MO2（CH3Cl）配合物可以异构化为更稳定的 CH3OM（O）Cl 分子，其中 CH3Cl 的 C-Cl 键添加到 MO2 的一个 O═M 键中。通过 MOx 机制的 C-Cl 活化通过计算的势能曲线进行解释。
