Unique structural trends in the lanthanoid oxocarbonyl complexes.
Unique structural trends in the lanthanoid oxocarbonyl complexes.
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DOI：
10.1021/ic800112d
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发表时间：
2008-04
影响因子：
4.6
通讯作者：
Ling Jiang;Xin-bo Zhang;Song Han;Qiang Xu
中科院分区：
文献类型：
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作者：
Ling Jiang;Xin-bo Zhang;Song Han;Qiang Xu
本文用基体分离红外光谱研究了激光烧蚀镧系元素原子（放射性Pm除外）与二氧化碳分子在固体氩中的反应。同位素位移，混合同位素分裂模式，和四氯化碳掺杂实验的基础上，镧系氧羰基配合物已被确定。对这些产物进行了密度泛函理论计算，支持了红外光谱的实验归属。红外光谱研究表明，早期镧系元素（La-Sm）羰基配合物为反式构型，铕和镱的羰基配合物为侧键构型（Eu-（eta 2-OC）O和Yb-（eta 2-OC）O），晚期镧系元素（Gd-Lu）的羰基配合物为顺式构型。自然键轨道分析表明，镧系元素羰基配合物的形成涉及到促进6s和4f电子进入金属价层。
Reactions of laser-ablated lanthanoid atoms (except for radioactive Pm) with carbon dioxide molecules in solid argon have been investigated using matrix-isolation infrared spectroscopy. On the basis of isotopic shifts, mixed isotopic splitting patterns, and CCl4-doping experiments, the lanthanoid oxocarbonyl complexes have been identified. Density functional theory calculations have been performed on these products, which support the experimental assignments of the infrared spectra. Infrared spectroscopic studies of these lanthanoid complexes combined with theoretical calculations reveal that the early lanthanoid (La-Sm) oxocarbonyl complexes adopt trans configurations, the europium and ytterbium ones adopt side-on-bonded modes (Eu-(eta2-OC)O and Yb-(eta2-OC)O), and the late lanthanoid (Gd-Lu) ones adopt cis configurations. Natural bond orbital analysis indicates that the formation of the lanthanoid oxocarbonyl complexes involves the promotion of 6s and 4f electrons into the metal valence shell.