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Solution-Phase Synthesis of a Base-Free Benzoborirene and a Three-Dimensional Inorganic Analogue.
Zhang, Hui; Wang, Junyi; Yang, Weiguang; Xiang, Libo; Sun, Weicheng; Ming, Wenbo; Li, Yinxin; Lin, Zhenyang; Ye, Qing.
Affiliation
  • Zhang H; Department of Chemistry, Southern University of Science and Technology, 518055 Shenzhen, P. R. China.
  • Wang J; School of Chemistry and Chemical Engineering, Harbin Institute of Technology, 150001 Harbin, P. R. China.
  • Yang W; Department of Chemistry, Southern University of Science and Technology, 518055 Shenzhen, P. R. China.
  • Xiang L; Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, 999077 Kowloon, Hong Kong.
  • Sun W; Department of Chemistry, Southern University of Science and Technology, 518055 Shenzhen, P. R. China.
  • Ming W; Department of Chemistry, Southern University of Science and Technology, 518055 Shenzhen, P. R. China.
  • Li Y; Department of Chemistry, Southern University of Science and Technology, 518055 Shenzhen, P. R. China.
  • Lin Z; Department of Chemistry, Southern University of Science and Technology, 518055 Shenzhen, P. R. China.
  • Ye Q; Department of Chemistry, Southern University of Science and Technology, 518055 Shenzhen, P. R. China.
J Am Chem Soc ; 142(41): 17243-17249, 2020 10 14.
Article in En | MEDLINE | ID: mdl-32941023
ABSTRACT
The base-free benzoborirene 1,2-BR-1,2-C6H4 (7) and its three-dimensional inorganic analogue 1,2-BR-1,2-C2B10H10 (13) have been successfully synthesized by Cp2ZrBr2 and LiCl elimination, respectively. The Cl analogue of the key intermediate for the formation of benzoborirene 7 has been isolated and structurally characterized, thus suggesting the reaction pathway via benzyne Zr complex formation, B-Br/Cbenzyne-Zr σ-bond metathesis, and a Cp2ZrBr2 elimination/ring-closing process. The rationality of the reaction pathway has been confirmed by DFT calculations. In addition, the title compounds shared the same reactivity pattern (i.e., 1,3-silyl migration) toward MeIiPr (8), thus allowing for the synthetic approach to the first carborane-substituted iminoborane 14.
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Full text: 1 Collection: 01-internacional Database: MEDLINE Language: En Journal: J Am Chem Soc Year: 2020 Type: Article
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Full text: 1 Collection: 01-internacional Database: MEDLINE Language: En Journal: J Am Chem Soc Year: 2020 Type: Article