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Scandium terminal imido complex induced intramolecular C-N bond cleavage and transformation

Science China Chemistry volume 57, pages 1098–1105 (2014)Cite this article

Abstract

The scandium terminal imido complex supported by a monoanionic tetradentate NNNN ligand, [LSc=N(DIPP)] (L = [MeC(N(DIPP))CHC(Me)(NCH2CH2N(Me)CH2CH2NMe2]−, DIPP = 2,6-(iPr)2C6H3) (1), undergoes a C-N bond cleavage at elevated temperature to give a mononuclear scandium anilido intermediate 2a, which subsequently aggregates into a binuclear scandium anilido complex 2. The mononuclear intermediate 2a reacts with alkyne or imine to provide two scandium anilido complexes 3 and 4, which contain a dianionic tetradentate NNNC ligand or a dianionic tetradentate NNNN ligand. DFT calculations on the reaction mechanism of C-N bond cleavage in 1 were also performed.

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Authors and Affiliations

  1. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, China

    JiaXiang Chu, QingHai Zhou, YuXue Li, XueBing Leng & YaoFeng Chen

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  1. JiaXiang Chu
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  2. QingHai Zhou
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  3. YuXue Li
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  4. XueBing Leng
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  5. YaoFeng Chen
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Correspondence to YuXue Li or YaoFeng Chen.

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Dedicated to Professor Qian Changtao on the occasion of his 80th birthday.

LI YuXue obtained his B.Sc. from Hebei Normal University in 1997, and his Ph.D. from Beijing Normal University in 2002. From 2002 to 2004, he worked as a postdoctoral fellow at Peking University and later as a research associate in Hong Kong University of Science and Technology. He joined Shanghai Institute of Organic Chemistry (SIOC) as an associate research professor in 2004, and became a research professor in 2011. His research interest is theoretical study on reaction mechanisms.

CHEN YaoFeng received his B.Sc. degree from Hangzhou Normal Colleague in 1993, M.Sc. from Hangzhou University in 1996 under the supervision of Prof. Yuqiu Gong, and Ph.D. from Zhejiang University in 1999 under the supervision of Prof. Zhiquan Shen. He did postdoctoral research in Shanghai Institute of Organic Chemistry (Prof. Changtao Qian’s group, 1999–2002), University of Montreal (Prof. Zargarian Davit’s group, 2002–2003), and University of California, Santa Barbara (Prof. Guillermo C. Bazan’s group, 2003–2005). He joined Shanghai Institute of Organic Chemistry as a research professor in 2006. His research interest is synthesis and reactivity of transition-metal complexes, especially the organometallic complexes of rare-earth metal.

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Chu, J., Zhou, Q., Li, Y. et al. Scandium terminal imido complex induced intramolecular C-N bond cleavage and transformation. Sci. China Chem. 57, 1098–1105 (2014). https://doi.org/10.1007/s11426-014-5117-8

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  • DOI: https://doi.org/10.1007/s11426-014-5117-8

Keywords

  • C-N bond cleavage
  • DFT calculation
  • imido complex
  • scandium