Issue 21, 2022

Decisive role of non-rare earth metals in high-regioselectivity addition of μ3-carbido clusterfullerene

Abstract

Endohedral clusterfullerenes featuring encapsulation of metal clusters which transfer electrons to the outer fullerene cages show intriguing chemical properties different from empty fullerenes. Despite the extensive studies on the chemical properties of empty fullerenes, especially C60, chemical functionalization of endohedral clusterfullerenes has been less explored, and previous reports are primarily limited to the well-known metal nitride and carbide clusterfullerenes. Herein, we report the first chemical functionalization of an emerging endohedral clusterfullerene μ3-carbido clusterfullerene (abbreviated as μ3-CCF) bearing central μ3-C and Ti(IV) atoms forming a Ti[double bond, length as m-dash]C double bond. A μ3-CCF Dy2TiC@Ih-C80 is synthesized, and its molecular structure is unambiguously determined by single-crystal X-ray diffraction for the first time. A photochemical cycloaddition reaction of Dy2TiC@Ih-C80 with 2-adamantane-2,3-[3H]-diazirine (abbreviated as AdN2) is then carried out and only one monoadduct Dy2TiC@Ih-C80-Ad is obtained, indicating its high regioselectivity. According to the X-ray single-crystal structure of Dy2TiC@Ih-C80-Ad, the Ad moiety selectively attacks the [6,6]-bond (conjunction of two fused hexagons), which is adjacent to the Ti4+ ion instead of the two Dy3+ ions, affording a [6,6]-open addition pattern. Theoretical calculations unveil that the Ti(IV) ion plays a decisive role in high regioselectivity, and the formation of [6,6]-open Dy2TiC@Ih-C80-Ad is thermodynamically preferred. Contrarily, a similar reaction of a Ti(III)-containing nitride clusterfullerene Y2TiN@C80 with AdN2 is predicted to generate a different type of adduct with the addition sites adjacent to the Y3+ ion instead of the Ti3+ ion. This reveals the peculiarity of the chemical property of μ3-CCF resulting from the existence of the non-rare earth metal Ti with a high oxidation state.

Graphical abstract: Decisive role of non-rare earth metals in high-regioselectivity addition of μ3-carbido clusterfullerene

Supplementary files

Article information

Article type
Research Article
Submitted
05 Jūl. 2022
Accepted
07 Sept. 2022
First published
14 Sept. 2022

Inorg. Chem. Front., 2022,9, 5688-5696

Decisive role of non-rare earth metals in high-regioselectivity addition of μ3-carbido clusterfullerene

M. Chen, Y. Zhao, F. Jin, M. Li, R. Guan, J. Xin, Y. Yao, X. Zhao, G. Wang, Q. Zhang, S. Xie and S. Yang, Inorg. Chem. Front., 2022, 9, 5688 DOI: 10.1039/D2QI01442D

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements