Mononuclear thorium halide clusters ThX4 (X = F, Cl): gas-phase hydrolysis reactions
Mononuclear thorium halide clusters ThX4 (X = F, Cl): gas-phase hydrolysis reactions
复制标题
单核卤化钍簇 ThX4 (X = F, Cl)：气相水解反应
DOI：
10.1039/c8cp03071e
复制
发表时间：
2018
影响因子：
3.3
通讯作者：
Huang Xin
中科院分区：
文献类型：
--
作者：
Wang Bin;Xia Chan-Juan;Fang Hong-Lin;Chen Wen-Jie;Zhang Yong-Fan;Huang Xin
用密度泛函理论(DFT)方法研究了单核卤化钍簇合物ThX4(X=F，Cl)的气相水解反应。我们发现，ThCl4的水解比ThF4更容易。此外，它们的水解反应倾向于Th(OH)4的直接脱水途径，而不是ThOX2的进一步水解途径。ThCl4和MCl4(M=Ti、Zr、Hf)的水解反应有一定的差异。X-H⋯Y(X=F，Cl；Y=F，Cl和OH)氢键在水解反应的氢转移过程中起着重要作用。空间效应和成键的差异可能是导致上述金属卤化物水解度差异的重要因素。
Density functional theory (DFT) calculations have been performed to explore the gas-phase hydrolysis reaction of mononuclear thorium halide clusters ThX4 (X = F, Cl). We have found that the hydrolysis of ThCl4 is easier than that of ThF4. Furthermore, their hydrolysis reactions favor pathways of direct dehydration of Th(OH)4 instead of further hydrolysis of ThOX2. There are some differences between the hydrolysis of ThCl4 and that of MCl4 (M = Ti, Zr and Hf). The X–H⋯Y (X = F, Cl; Y = F, Cl and OH) hydrogen bonds play an important role in the hydrogen transfer process of the hydrolysis reaction. The differences in the steric effects and bonding may be important factors that are related to the disparities in the hydrolysis of the above-mentioned metal halides.