Burkhardt Jordan, Chen Teng-Teng, Chen Wei-Jia, Yuan Dao-Fu, Li Wan-Lu, Wang Lai-Sheng
Aiiso Yufeng Li Family Department of Chemical and Nano Engineering, University of California, San Diego, La Jolla, California 92093, United States.
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong (SAR) 999077, China.
Inorg Chem. 2024 Sep 16;63(37):17215-17224. doi: 10.1021/acs.inorgchem.4c02950. Epub 2024 Sep 4.
We report an investigation on the structures and chemical bonding in a series of di-lanthanum boron clusters, LaB ( = 4-6), using photoelectron spectroscopy and theoretical calculations. Well-resolved photoelectron spectra are obtained and used to verify the global minima of the lanthanide boron clusters. The structures of LaB and LaB are found to consist of open B and B rings, respectively, around the La dimer equatorially. Theoretical evidence of La-La σ bonding is obtained in LaB, whereas the bonding in LaB is similar to that of an incomplete inverse sandwich without real La-La bonding. The global minimum of LaB is completely different, where one of the La atoms can be viewed as substituting a B atom of the B cluster due to the high electronic stability of the B borozene. The resulting lanthaborozene [LaB] forms a half-sandwich structure with the second La atom, with evidence of La-La σ bonding. Lanthanide-lanthanide bonds are relatively rare in chemistry. The current work suggests that binary lanthanide boron clusters provide interesting systems to study lanthanide-lanthanide bonding.
我们报道了一项利用光电子能谱和理论计算对一系列二镧硼簇合物La₂Bₙ（n = 4 - 6）的结构和化学键进行的研究。获得了分辨良好的光电子能谱，并用于验证镧硼簇合物的全局极小值。发现La₂B₄和La₂B₅的结构分别由围绕La二聚体赤道的开放B₄和B₅环组成。在La₂B₄中获得了La - La σ键的理论证据，而La₂B₅中的键合类似于没有真正La - La键合的不完全反夹心结构。La₂B₆的全局极小值完全不同，由于B₆硼烯的高电子稳定性，其中一个La原子可视为取代了B₆簇中的一个B原子。由此产生的镧硼烯[LaB₆]与第二个La原子形成半夹心结构，并有La - La σ键的证据。镧 - 镧键在化学中相对罕见。目前的工作表明，二元镧硼簇合物为研究镧 - 镧键合提供了有趣的体系。
