Citation: Wei CHEN, Yongmei KANG, Jiaqi AN, Qi LIU, Yangjia FAN, Fanlong ZENG, Hongshan KE, Wenyuan WANG. Synthesis and structures of weakly coordinating anions of phenanthrenediolate with Si, Ge, Sn, and Sb[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(10): 2169-2178. doi: 10.11862/CJIC.20260046 shu

Synthesis and structures of weakly coordinating anions of phenanthrenediolate with Si, Ge, Sn, and Sb

College of Chemistry and Materials Science, Key Laboratory of Synthetic and Natural Functional Molecules of Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest University, Xi′an 710127, China

Corresponding author: Hongshan KE, hske@nwu.edu.cn Wenyuan WANG, wangwy@nwu.edu.cn
Received Date: 9 February 2026
Revised Date: 29 May 2026

Figures(6)

Bulky hexacoordinate anions, with main-group heavy elements as central atoms and fused-ring diphenols as ligands, can act as weakly coordinating ligands for the construction of novel functional coordination complexes with metals. In this work, reactions of 9, 10-phenanthrenequinone (C₁₄H₈O₂, 1) and sodium 9, 10-phenanthrenediolate (C₁₄H₈O₂Na₂, 2) with SiCl₄, GeCl₄, SnCl₂, and SbCl₃ were carried out, leading to the first isolation of compounds of octahedral weakly coordinating anions of Si, Ge, Sn, and Sb chelated by three phenanthrenediolate ligands, namely [Na(THF)₃]₂[Si(C₁₄H₈O₂)₃] (3), [Na(THF)₃]₂[Ge(C₁₄H₈O₂)₃] (4), [Na(THF)₃]₂[Sn(C₁₄H₈O₂)₃] (5), and Na[Sb(C₁₄H₈O₂)₃] (6). Further cation-exchange reactions of 6 yielded tris(9, 10-phenanthrenediolato)antimonate(Ⅴ) salts (7 and 8), with [Li(THF)₄]⁺ and Et₃NH⁺ as counterions, respectively. All products were characterized by ¹H and ¹³C NMR spectroscopy for composition and purity, and the structures of 3-5, 7, and 8 were determined by single-crystal X-ray diffraction. Structural analyses indicated that the core [EO₆] units (E=Si, Ge, Sn) in 3-5 have strong internal bonding but weak interactions with peripheral Na⁺ cations, showing pronounced outward weak coordination. In 7 and 8, non-coordinating cation-anion contacts yield an ideal symmetric [SbO₆] core, endowing the antimonate anion with greater resistance to cation perturbation.
- phenanthrenequinone,
- phenanthrene-9, 10-diol,
- silicon,
- germanium,
- tin,
- antimony,
- weakly coordinating anion
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