含有重14族元素配位原子配体的稀土配合物的合成、成键模式及反应性探究

稀土元素配合物的合成及理化性质研究一直受到国内外研究者的广泛关注。然而，目前所报道的稀土元素配合物中配体的配位原子几乎均为第一、二周期较轻元素，关于含有更重配位原子配体稀土元素配合物的相关研究目前仍然极为有限。在本次申请中，申请人拟结合之前在主族元素及稀土元素金属有机化学方面的研究积累，建立具有重14族元素（Si、Ge、Sn、Pb等）配位原子配体的稀土元素配合物的合成方法，并对其中配位键的成键模式及目标配合物的反应特性进行探究。相比于第一、二周期较轻元素，重14族元素具有主量子数更高的s及p原子轨道。这些轨道分布更加弥散，能量也更高，因此也有望与稀土元素中心展现出不同的成键相互作用并最终影响配合物的几何结构、电子构型及理化性能。

The synthesis and physical/chemical property studies of rare earth compounds have attracted increasing attention in China and abroad. However, coordinating atoms of the ligands in reported rare earth compounds were majorly first and second row light elements, such as nitrogen, oxygen, carbon, and hydrogen. Researches on rare earth compounds bearing ligands containing heavier coordinating atoms are still extremely limited. Based on our previous research experience on organometallic chemistry of main group element compounds and rare earth compounds, we plan to establish the synthetic method of rare earth compounds bearing ligands containing heavier group 14 coordinating atoms (such as Si, Ge, Sn and Pb) in this proposal. The nature of the coordinate bonds between rare earth centers and heavier group 14 elements and the reactivity of the target rare earth compounds will also be investigated. Compared to the lighter elements in the first and second row of the periodic table, heavier group 14 elements have s and p atomic orbitals with larger principal quantum numbers. These atomic orbitals show higher orbital energy and more diffused distribution, thus would better interact with the atomic orbitals with adequate symmetry of rare earth centers. Interesting coordination geometry, electron configuration and reactivity are expected based on this fundamental difference between lighter and heavier elements.