双(硅亚基)稳定的一价锑和一价铋阳离子的分离与特性研究。
Isolation and characterization of bis(silylene)-stabilized antimony(I) and bismuth(I) cations.
机构信息
State Key Laboratory and Institute of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, 94 Weijin Road, 300071, Tianjin, China.
Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, 211816, Nanjing, China.
出版信息
Nat Commun. 2023 May 23;14(1):2968. doi: 10.1038/s41467-023-38606-2.
Monovalent group 15 cations LPn + (L = σ-donor ligands, Pn = N, P, As, Sb, Bi) have attracted significant experimental and theoretical interest because of their unusual electronic structures and growing synthetic potential. Herein, we describe the synthesis of a family of antimony(I) and bismuth(I) cations supported by a bis(silylene) ligand [(TBDSi)Pn][BAr] (TBD = 1, 8, 10, 9-triazaboradecalin; Ar = 3,5-CF-CH; Pn = Sb, (2); Bi, (3)). The structures of 2 and 3 have been unambiguously characterized spectroscopically and by X-ray diffraction analysis and DFT calculations. They feature bis-coordinated Sb and Bi atoms which exhibit two lone pairs of electrons. The reactions of 2 and 3 with methyl trifluoromethane sulfonate provide a approach for the preparation of dicationic antimony(III) and bismuth(III) methyl complexes. Compounds 2 and 3 serve as 2e donors to group 6 metals (Cr, Mo), giving rise to ionic antimony and bismuth metal carbonyl complexes 6-9.
单价 15 族阳离子 LPn + （L = σ-给体配体，Pn = N、P、As、Sb、Bi）因其独特的电子结构和不断增长的合成潜力引起了人们的极大关注。在此，我们描述了一系列由双（硅烯）配体 [(TBDSi)Pn][BAr] （TBD = 1,8,10,9-四氮杂硼杂环十二烷；Ar = 3,5-CF-CH；Pn = Sb，（2）；Bi，（3））支持的锑（I）和铋（I）阳离子的合成。2 和 3 的结构已通过光谱学、X 射线衍射分析和 DFT 计算得到明确表征。它们具有双配位的 Sb 和 Bi 原子，其特征是具有两对孤对电子。2 和 3 与甲基三氟甲烷磺酸酯的反应为制备三价锑（III）和铋（III）甲基配合物提供了一种方法。化合物 2 和 3 作为 2e 供体与第 6 族金属（Cr、Mo）反应，生成离子锑和铋金属羰基配合物 6-9。
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