Zhao Li-Juan, Xu Hong-Guang, Xu Xi-Ling, Zheng Wei-Jun
Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
University of Chinese Academy of Sciences, Beijing 100049, China.
J Phys Chem Lett. 2023 Mar 23;14(11):2854-2861. doi: 10.1021/acs.jpclett.3c00207. Epub 2023 Mar 14.
Unlike C≡O, which is common in coordination chemistry and organometallic chemistry, little is known about Si≡O or Ge≡O compounds. Here we report a GeO cluster featuring a Ge≡O triple bond. The structural and chemical bonding properties of GeO are investigated using anion photoelectron spectroscopy and theoretical calculations. Two nearly degenerate isomers have been found for GeO. The lowest-energy structure (6A) can be viewed as an O atom bonding with a tetragonal bipyramidal Ge. The second one (6B) can be considered as an O atom interacting with a capped trigonal bipyramidal Ge. Chemical bonding analyses reveal that GeO (6A) can be viewed as a Ge≡O unit interacting with a σ antiaromatic symmetric tetragonal pyramidal Ge moiety. Comparisons of the chemical bonding in GeO (6A) with that in GeCO and GeMnO indicate the similar behavior of Ge≡O to C≡O and Mn≡O in its bonding to the Ge and Ge moieties.
与在配位化学和有机金属化学中常见的C≡O不同，人们对Si≡O或Ge≡O化合物知之甚少。在此，我们报道了一种具有Ge≡O三键的GeO簇合物。利用阴离子光电子能谱和理论计算研究了GeO的结构和化学键性质。已发现GeO有两种近简并异构体。能量最低的结构（6A）可看作是一个O原子与一个四方双锥Ge键合。第二个结构（6B）可认为是一个O原子与一个盖帽三角双锥Ge相互作用。化学键分析表明，GeO（6A）可看作是一个Ge≡O单元与一个σ反芳香性对称四方锥Ge部分相互作用。将GeO（6A）中的化学键与GeCO和GeMnO中的化学键进行比较，表明Ge≡O在与Ge和Ge部分键合时的行为与C≡O和Mn≡O相似。
