In:
Inorganic Chemistry Frontiers, Royal Society of Chemistry (RSC), Vol. 9, No. 21 ( 2022), p. 5688-5696
Kurzfassung:
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 C 60 , 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 μ 3 -carbido clusterfullerene (abbreviated as μ 3 -CCF) bearing central μ 3 -C and Ti( iv ) atoms forming a TiC double bond. A μ 3 -CCF Dy 2 TiC@ I h -C 80 is synthesized, and its molecular structure is unambiguously determined by single-crystal X-ray diffraction for the first time. A photochemical cycloaddition reaction of Dy 2 TiC@ I h -C 80 with 2-adamantane-2,3-[3 H ]-diazirine (abbreviated as AdN 2 ) is then carried out and only one monoadduct Dy 2 TiC@ I h -C 80 -Ad is obtained, indicating its high regioselectivity. According to the X-ray single-crystal structure of Dy 2 TiC@ I h -C 80 -Ad, the Ad moiety selectively attacks the [6,6]-bond (conjunction of two fused hexagons), which is adjacent to the Ti 4+ ion instead of the two Dy 3+ 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 Dy 2 TiC@ I h -C 80 -Ad is thermodynamically preferred. Contrarily, a similar reaction of a Ti( iii )-containing nitride clusterfullerene Y 2 TiN@C 80 with AdN 2 is predicted to generate a different type of adduct with the addition sites adjacent to the Y 3+ ion instead of the Ti 3+ ion. This reveals the peculiarity of the chemical property of μ 3 -CCF resulting from the existence of the non-rare earth metal Ti with a high oxidation state.
Materialart:
Online-Ressource
ISSN:
2052-1553
Sprache:
Englisch
Verlag:
Royal Society of Chemistry (RSC)
Publikationsdatum:
2022
