Reactions of late lanthanide metal atoms and methanol in solid argon: a matrix isolation infrared spectroscopic and theoretical study.
Reactions of late lanthanide metal atoms and methanol in solid argon: a matrix isolation infrared spectroscopic and theoretical study.
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DOI：
10.1021/jp209135a
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发表时间：
2011-12
期刊：
影响因子：
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通讯作者：
Yu Gong;L. Andrews;Mingyang Chen;D. Dixon
中科院分区：
文献类型：
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作者：
Yu Gong;L. Andrews;Mingyang Chen;D. Dixon
采用密度泛函理论的方法，结合基体隔离红外光谱和电子结构计算，研究了激光烧蚀后镧系元素原子与甲醇的反应。铽和镥原子与甲醇自发反应形成CH（3）OTbH和CH（3）OLuH插入产物，其进一步与另一个甲醇分子反应得到Tb（OCH（3））（2）和Lu（OCH（3））（2）产物，如先前在铀中发现的。Dy通过Yb和甲醇的反应首先在样品退火期间产生Ln（CH（3）OH）络合物，其在可见光照射下异构化为CH（3）OLnH插入产物。CH（3）OLnH分子的Ln-H伸缩振动频率呈现出从Tb到Lu的独特趋势，这一结果也在B3 LYP水平上得到了再现.虽然CH（3）LnOH分子被预测比O-H键插入产物更稳定，但如计算的势能面所揭示的，C-O键插入异构体的形成在动力学上被禁止。
The reactions of laser-ablated late lanthanide atoms and methanol were studied using matrix isolation infrared spectroscopy and electronic structure calculations at the density functional theory level. Both terbium and lutetium atoms react with methanol spontaneously to form the CH(3)OTbH and CH(3)OLuH insertion products, which react further with another methanol molecule to give the Tb(OCH(3))(2) and Lu(OCH(3))(2) products as found previously for uranium. The reactions of Dy through Yb and methanol first produce Ln(CH(3)OH) complexes during sample annealing, which isomerize to the CH(3)OLnH insertion products on visible irradiation. The Ln-H stretching frequencies of the CH(3)OLnH molecules exhibit a unique trend from Tb to Lu, which is also reproduced by theoretical calculations at the B3LYP level of theory. Although the CH(3)LnOH molecules are predicted to be more stable than the O-H bond insertion products, formation of the C-O bond insertion isomers is kinetically prohibited as revealed by calculated potential energy surfaces.