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Endohedral fullerene with μ3-carbido ligand and titanium-carbon double bond stabilized inside a carbon cage

Author

Listed:
  • A. L. Svitova

    (Leibniz Institute for Solid State and Materials Research Dresden, Helmholtzstrasse 20)

  • K. B. Ghiassi

    (University of California)

  • C. Schlesier

    (Leibniz Institute for Solid State and Materials Research Dresden, Helmholtzstrasse 20)

  • K. Junghans

    (Leibniz Institute for Solid State and Materials Research Dresden, Helmholtzstrasse 20)

  • Y. Zhang

    (Leibniz Institute for Solid State and Materials Research Dresden, Helmholtzstrasse 20)

  • M. M. Olmstead

    (University of California)

  • A. L. Balch

    (University of California)

  • L. Dunsch

    (Leibniz Institute for Solid State and Materials Research Dresden, Helmholtzstrasse 20)

  • A. A. Popov

    (Leibniz Institute for Solid State and Materials Research Dresden, Helmholtzstrasse 20)

Abstract

In all metallofullerenes known before this work, metal atoms form single highly polar bonds with non-metal atoms in endohedral cluster. This is rather surprising for titanium taking into account the diversity of organotitanium compounds. Here we show that the arc-discharge synthesis of mixed titanium-lutetium metallofullerenes in the presence of ammonia, melamine or methane unexpectedly results in the formation of TiLu2C@Ih-C80 with an icosahedral Ih(7) carbon cage. Single-crystal X-ray diffraction and spectroscopic studies of the compound reveal an unprecedented endohedral cluster with a μ3-carbido ligand and Ti-C double bond. The Ti(IV) in TiLu2C@Ih-C80 can be reversibly reduced to the Ti(III) state. The Ti=C bonding and Ti-localized lowest unoccupied molecular orbital in TiLu2C@Ih-C80 bear a certain resemblance to titanium alkylidenes. TiLu2C@Ih-C80 is the first metallofullerene with a multiple bond between a metal and the central, non-metal atom of the endohedral cluster.

Suggested Citation

  • A. L. Svitova & K. B. Ghiassi & C. Schlesier & K. Junghans & Y. Zhang & M. M. Olmstead & A. L. Balch & L. Dunsch & A. A. Popov, 2014. "Endohedral fullerene with μ3-carbido ligand and titanium-carbon double bond stabilized inside a carbon cage," Nature Communications, Nature, vol. 5(1), pages 1-8, May.
    • Handle: RePEc:nat:natcom:v:5:y:2014:i:1:d:10.1038_ncomms4568
    DOI: 10.1038/ncomms4568
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    Cited by:

    1. Qingyu Meng & Laura Abella & Yang-Rong Yao & Dumitru-Claudiu Sergentu & Wei Yang & Xinye Liu & Jiaxin Zhuang & Luis Echegoyen & Jochen Autschbach & Ning Chen, 2022. "A charged diatomic triple-bonded U≡N species trapped in C82 fullerene cages," Nature Communications, Nature, vol. 13(1), pages 1-10, December.
    2. Runnan Guan & Jing Huang & Jinpeng Xin & Muqing Chen & Pingwu Du & Qunxiang Li & Yuan-Zhi Tan & Shangfeng Yang & Su-Yuan Xie, 2024. "A stabilization rule for metal carbido cluster bearing μ3-carbido single-atom-ligand encapsulated in carbon cage," Nature Communications, Nature, vol. 15(1), pages 1-8, December.

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