Citation: Jing-Jing LIU, Jian-Xuan SHANG, Yan GUO, Fang-Fang GAO, Jing WEI, Fan-Long ZENG, An-Yang LI, Wen-Yuan WANG. Structural Characterizations for Two-Coordinate β-Diketiminato Gallium(Ⅰ) Carbene Analogue Synthesized via Reduction[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(5): 843-849. doi: 10.11862/CJIC.2022.101 shu

Structural Characterizations for Two-Coordinate β-Diketiminato Gallium(Ⅰ) Carbene Analogue Synthesized via Reduction

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 710054, 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: Wen-Yuan WANG, wangwy@nwu.edu.cn
Received Date: 2 December 2021
Revised Date: 1 March 2022

Figures(5)

The β-diketiminate ligands without substituents containing active sites exhibit good electron stabilization effect and sterically protection for the low-valent metal center. Potassium was able to reduce β-diketiminato gallium(Ⅲ) dichloride PhC(PhCN-Dip)₂GaCl₂ (2, Dip=2, 6-ⁱPr₂C₆H₃) to highly yield a new β-diketiminato gallium(Ⅰ) carbene analogue PhC(PhCN-Dip)₂ Ga: (3) as a monomeric molecule. The structures and composition of compounds 2 and 3 were characterized by the X-ray single-crystal diffraction and the NMR spectroscopies. The central Ga(Ⅰ) ion of 3 occupies a point angle of the six-membered N-heterocyclic plane with a distorted two-coordinate geometry. Theoretical calculations show that the HOMO corresponded to the lone pair electrons at the Ga center, which had a low energy level of -6.352 eV, while the LUMO+1 was associated with the empty p-orbital of Ga with an energy of 601.0 kJ·mol^-1 higher than the HOMO, indicating that 3 is a gallium(Ⅰ) carbene analogue and isostructural to N-heterocyclic carbene, and the lone pair of Ga(Ⅰ) ion has good thermal stability. CCDC: 2123086, 2; 2123087, 3.
- β-diketiminate,
- reduction,
- gallium(Ⅰ) carbene analogue,
- low coordination complex
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