Synthesis and Structural Characterization of Carbene-Stabilized Carborane-Fused Azaborolyl Radical Cation and Dicarbollyl-Fused Azaborole

详细信息    查看全文

• 作者：Hao Wang ; Jiji Zhang ; Zhenyang Lin ; Zuowei Xie
• 刊名：Organometallics
• 出版年：2016
• 出版时间：August 22, 2016
• 年：2016
• 卷：35
• 期：16
• 页码：2579-2582
• 全文大小：312K
• 年卷期：0
• ISSN：1520-6041

文摘

The carbene-stabilized electron-rich iminocarboranyl boron(I) compound [(Dipp)NC(Bu^t)C₂B₁₀H₁₀]B(NHC) (1) (Dipp = 2,6-diisopropylphenyl, NHC = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) is an excellent precursor for the preparation of the unprecedented carborane-fused azaborolyl radical cation [{(Dipp)NC(Bu^t)C₂B₁₀H₁₀}B(NHC)]^•+ ([2]^•+) and dicarbollyl-fused azaborole 7,8-nido-C₂B₉H₉-7,8-C(Bu^t)N(Dipp)B(NHC) (3) via controlled single-electron oxidation and two-electron oxidative deboration, respectively. Single-crystal X-ray analyses and DFT calculations indicate that the unpaired electron in [2]^•+ is delocalized over the BNC unit, and the two fused five-membered rings in 3 form a sort of π-conjugated system.