Zhang Naixin, Wu Qunyan, Lan Jianhui, Shi Weiqun, Wang Congzhi
College of Nuclear Science and Technology, Harbin Engineering University, Harbin 150001, China.
Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China.
Molecules. 2024 Dec 9;29(23):5815. doi: 10.3390/molecules29235815.
The aromatic boron cluster B () has similar π bonding to CH, which is named "borozene". The B ligand has been observed to stabilize monovalent Ln(+I) in -LnB (Ln = La, Pr, Tb, Tm, and Yb) borozene complexes. Low-valency actinide complexes have been reported more rarely, and B may be one of the potential ligands. Here, we report a theoretical study on a series of actinide metal-doping octa-boron clusters AnB (An = Pa, U, Np, and Pu). It was found that each species has both half-sandwich and chair-like structures. Except for PaB, the half-sandwich structures of UB, NpB, and PuB are more energetically stable than the chair-like structures, and the half-sandwich clusters of AnB are found to be actinide(II) borozene complexes with the M[B] type. For each of the half-sandwich clusters, the B ligand has σ and π double aromaticity. Various bonding analyses of AnB confirm the covalent interactions between the doped actinide metals and the octa-boron clusters, which further stabilize the complexes and determine the relative stability of AnB. As expected, these complexes show high bond dissociation energies, especially PaB with stronger Pa-B covalent bonds. These results demonstrate that the B doubly aromatic ligand is able to stabilize divalent actinides.
芳香硼簇合物B（）具有与CH类似的π键，被命名为“硼苯”。已观察到B配体在-LnB（Ln = La、Pr、Tb、Tm和Yb）硼苯配合物中能稳定一价Ln（+I）。低价锕系元素配合物的报道较少，而B可能是潜在配体之一。在此，我们报道了一系列锕系金属掺杂八硼簇合物AnB（An = Pa、U、Np和Pu）的理论研究。发现每个物种都具有半夹心结构和椅状结构。除PaB外，UB、NpB和PuB的半夹心结构在能量上比椅状结构更稳定，并且发现AnB的半夹心簇是具有M[B]类型的锕系（II）硼苯配合物。对于每个半夹心簇，B配体具有σ和π双重芳香性。对AnB的各种键合分析证实了掺杂的锕系金属与八硼簇之间的共价相互作用，这进一步稳定了配合物并确定了AnB的相对稳定性。正如预期的那样，这些配合物显示出高的键解离能，特别是PaB具有更强的Pa - B共价键。这些结果表明，B双重芳香配体能够稳定二价锕系元素。
