Citation: Jiaqi AN, Yunle LIU, Jianxuan SHANG, Yan GUO, Ce LIU, Fanlong ZENG, Anyang LI, Wenyuan WANG. Reactivity of extremely bulky silylaminogermylene chloride and bonding analysis of a cubic tetragermylene[J]. Chinese Journal of Inorganic Chemistry, ;2024, 40(8): 1511-1518. doi: 10.11862/CJIC.20240072 shu

Reactivity of extremely bulky silylaminogermylene chloride and bonding analysis of a cubic tetragermylene

Jiaqi AN ¹ ,
Yunle LIU ¹ ,
Jianxuan SHANG ² ,
Yan GUO ³ ,
Ce LIU ¹ ,
Fanlong ZENG ¹ ,
Anyang LI ^1,, ,
Wenyuan WANG ^1,,

1.
College of Chemistry and Materials Science, Key Laboratory of Synthetic and Natural Functional Molecule of Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest University, Xi'an 710127, China
2.
Shaanxi Coal and Chemical Industry Group Co., Ltd., Xi'an 710100, China
3.
State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, National Demonstration Center for Experimental Chemistry Education, College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China

Corresponding author: Anyang LI, Liay@nwu.edu.cn Wenyuan WANG, wangwy@nwu.edu.cn
Received Date: 3 March 2024
Revised Date: 3 April 2024

Figures(5)

The low-valent germanium compounds with ultra-bulky silylamino groups can construct novel chemical structures and provide new discoveries with academic importance. The two-coordinated ultra-bulky silylamino germylene chloride Ge(N(SiⁱPr₃)₂)Cl (1) has an empty 4p-orbital and a lone pair. Two reactions of thermal structural conversion and oxidation addition with phenanthrenequinone on the two activities of 1 were investigated. The thermal decomposition of 1 generated tetragermylene Ge₄(NSiⁱPr₃)₄ (2) with cubic molecular structure, and its oxidative addition quantitatively with phenanthrenequinone (L) furnished aminomonochlorogermanium(IV) phenanthren-9, 10-diolate: [Ge(N(SiⁱPr₃)₂)(L)Cl] (3). Their single-crystal structures and composition were fully characterized. Tetragermylene 2 is essentially a tetrameric adduct of isogermanitrile, its molecular structure exhibits a distorted cubic configuration, and four Ge atoms and four N atoms exist at the eight vertices of the central cubic skeleton. The Ge—N bond length is 0.2036(3) nm, the bond angles of N—Ge—N and Ge—N—Ge are 85.51(18)° and 94.32(16)°, respectively, and the side of the cubic skeleton is close to a planar parallelogram. Theoretical calculation reveals for the first time the bonding of 2. The natural bond orbital (NBO) investigation provided a total of 20 molecular orbitals on the Ge₄N₄ skeleton. Additionally, the localized orbitals presented three energy levels of -12.22, -15.12, and -20.12 eV, for four Ge lone pairs, 12 Ge—N bonds and four Si—N bonds, respectively. The Ge lone pair mainly remains the 4s character, while the Ge—N bond is contributed by the orbitals of 2s (18.4%) and 2p (71.3%) on N atom, 4s (0.75%) and 4p (9.43%) on Ge atom. In the molecule of 3, the sp³ hybridized Ge^Ⅳ is coordinated by four donor atoms and exhibits a distorted tetrahedral configuration, because of the steric hindrance and asymmetric bonding.
- ultra-bulky silylamino group,
- isonitrile,
- germylene,
- cubic configuration
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