Multiple Bonding in Lanthanides and Actinides: Direct Comparison of Covalency in Thorium(IV)- and Cerium(IV)-Imido Complexes
Multiple Bonding in Lanthanides and Actinides: Direct Comparison of Covalency in Thorium(IV)- and Cerium(IV)-Imido Complexes
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DOI：
10.1021/jacs.9b04061
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发表时间：
2019-06-12
影响因子：
15
通讯作者：
Schelter, Eric J.
中科院分区：
文献类型：
--
作者：
Cheisson, Thibault;Kersey, Kyle D.;Schelter, Eric J.
合成并表征了一系列亚氨基钍配合物。广泛的实验和计算比较的同构铈（IV）-亚氨基配合物揭示了一个显着更多的共价键的安排相比，更多的离子Th=N键的Ce=N键。钍-亚氨基部分被观察到是3个数量级以上的基本比它们的铈同系物。更一般地说，这些结果提供了独特的实验证据，为更大的共价特性的4f度5d度Ce（IV）的多重键相比，其5 f度6d度Th（IV）的锕系同源物。
A series of thorium(IV)-imido complexes was synthesized and characterized. Extensive experimental and computational comparisons with the isostructural cerium(IV)-imido complexes revealed a notably more covalent bonding arrangement for the Ce=N bond compared with the more ionic Th=N bond. The thorium-imido moieties were observed to be 3 orders of magnitude more basic than their cerium congeners. More generally, these results provide unique experimental evidence for the larger covalent character of 4f degrees 5d degrees Ce(IV) multiple bonds compared to its 5f degrees 6d degrees Th(IV) actinide congener.