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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Actinide (An = Th-Pu) dimetallocenes: promising candidates for metal-metal multiple bonds
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Actinide (An = Th-Pu) dimetallocenes: promising candidates for metal-metal multiple bonds

机译：in系元素（An = Th-Pu）二茂金属：金属-金属多重键的有希望的候选物

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摘要

Synthesis of complexes with direct actinide-actinide (An-An) bonding is an experimental 'holy grail' in actinide chemistry. In this work, a series of actinide dimetallocenes An(2)Cp(2)* (Cp* = C-5(CH3)(5), An = Th-Pu) with An-An multiple bonds have been systematically investigated using quantum chemical calculations. The coaxial Cp*-An-An-Cp* structures are found to be the most stable species for all the dimetallocenes. A Th-Th triple bond is predicted in the Th2Cp2* complex, and the calculated An-An bond orders decrease across the actinide series from Pa to Pu. The covalent character of the An-An bonds is analyzed by using natural bond orbitals (NBO), molecular orbitals (MO), the quantum theory of atoms in molecules (QTAIM), and electron density difference (EDD). While Th 6d orbitals dominate the Th-Th bonds in Th2Cp2*, the An 6d-orbital characters decrease and 5f-orbital characters increase for complexes from Pa2Cp2* to Pu2Cp2*. All these actinide dimetallocenes are stable in the gas phase relative to the AnCp* reference at room temperature. Based on the reactions of AnCp(2)* and An, Th2Cp2*, Pa2Cp2* and possibly also U2Cp2* should be accessible as isolated molecules under suitable synthetic conditions. Our results shed light on the molecular design of ligands for stabilizing actinide-actinide multiple bonds.
机译：具有直接act系元素-act系元素（An-An）键的配合物的合成是act系元素化学中的实验“圣杯”。在这项工作中，一系列的quantum系双金属茂An（2）Cp（2）*（Cp * = C-5（CH3）（5），An = Th-Pu）具有An-An多个键已通过量子系统地研究。化学计算。发现同轴Cp * -An-An-Cp *结构是所有二茂金属最稳定的物种。在Th2Cp2 *配合物中预测有Th-Th三键，并且从Pa到Pu的整个across系元素序列，计算出的An-An键序降低。通过使用自然键轨道（NBO），分子轨道（MO），分子中原子的量子理论（QTAIM）和电子密度差（EDD）分析An-An键的共价特征。当Th 6d轨道在Th2Cp2 *中的Th-Th键上占主导地位时，从Pa2Cp2 *到Pu2Cp2 *的配合物，An 6d轨道特征减少而5f轨道特征增加。相对于室温下的AnCp *参考，所有这些系元素二茂金属在气相中都是稳定的。根据AnCp（2）*与An的反应，在合适的合成条件下，Th2Cp2 *，Pa2Cp2 *以及可能的U2Cp2 *应该可以作为分离的分子得到。我们的结果为稳定act系元素-act系元素多键配体的分子设计提供了启示。

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