1,3-Butadienyl Dianions as Non-Innocent Ligands: Synthesis and Characterization of Aromatic Dilithio Rhodacycles.
1,3-Butadienyl Dianions as Non-Innocent Ligands: Synthesis and Characterization of Aromatic Dilithio Rhodacycles.
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DOI：
10.1002/anie.201504521
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发表时间：
2015-08
影响因子：
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通讯作者：
Junnian Wei;Yonglian Zhang;Wen‐Xiong Zhang;Z. Xi
中科院分区：
文献类型：
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作者：
Junnian Wei;Yonglian Zhang;Wen‐Xiong Zhang;Z. Xi
在此，我们报道了 1,4-二锂基-1,3-丁二烯（1,3-丁二烯基二价阴离子的一种）可以充当非无害配体，从低价过渡金属中获取电子。二锂试剂与[{RhCl(cod)}2]反应得到二锂铑环3a。单晶X射线结构分析揭示了具有平均键长的3a的结构。 XPS数据表明3a中Rh的氧化态更可能是Rh(3+)。 CDA/ECDA 证实了电子转移过程。 (7)3a的Li核磁共振谱和理论计算揭示了相当大的芳香特征。在此过程中，二锂化合物充当非无害配体和正式氧化剂。这些结果表明具有合适π共轭的有机锂化合物可以用作电子受体。
Herein we report that 1,4-dilithio-1,3-butadienes, a type of 1,3-butadienyl dianion, can act as non-innocent ligands, taking electrons from low-valent transition metals. Dilithio reagents reacted with [{RhCl(cod)}2] to give dilithio rhodacycle 3 a. Single-crystal X-ray structural analysis revealed the structure of 3 a with averaged bond lengths. XPS data suggested that the oxidation state of Rh in 3 a was more likely to be Rh(3+). CDA/ECDA confirmed the electron-transfer process. (7)Li NMR spectra of 3 a and theoretical calculations revealed a considerable aromatic character. In this process, the dilithio compounds behaved as non-innocent ligands and formal oxidants. These results demonstrated that organolithium compounds with suitable π-conjugation could be used as electron acceptor.