Sc[subscript 3]N@(C[subscript 80]-I[subscript h](7))(CF[subscript 3])[subscript 14] and Sc[subscript 3]N@(C[subscript 80]-I[subscript h](7))CF[subscript 3])[subscript 16]. Endohedral Metallofullerene Derivatives with Exohedral Addends on Four and Eight Triple-Hexagon Junctions. Does the Sc[subscript 3]N Cluster Control the Addition Pattern or Vice Versa?
The compounds Sc{sub 3}N{at}(C{sub 80}-I{sub h}(7))(CF{sub 3}){sub 14} (1) and Sc{sub 3}N{at}(C{sub 80}-I{sub h}(7))(CF{sub 3}){sub 16} (2) were prepared by heating Sc{sub 3}N{at}C{sub 80}-I{sub h}(7) and Ag(CF{sub 3}CO{sub 2}) to 350 C in a sealed tube. The structures of 1 and 2 were determined by single-crystal X-ray diffraction. They are the first X-ray structures of any endohedral metallofullerene with more than four cage C(sp{sup 3}) atoms. The structures exhibit several unprecedented features for metallic nitride fullerenes, including multiple cage sp{sup 3} triple-hexagon junctions (four on 1 and eight on 2), no cage disorder and little (2) or no (1) endohedral atom disorder, high-precision (C-C esd's are 0.005 {angstrom} for 1 and 0.002 {angstrom} for 2), an isolated aromatic C(sp{sup 2}){sub 6} hexagon on 2, and two negatively charged isolated aromatic C(sp{sup 2}){sub 5}{sup -} pentagons on 2 that are bonded to one of the Sc atoms. DFT calculations are in excellent agreement with the two Sc{sub 3}N conformations observed for 2 ({Delta}E(calc) = 0.36 kJ mol{sup -1}; {Delta}E(exp) = 0.26(2) kJ mol{sup -1}).
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 1006001
- Journal Information:
- J. Am. Chem. Soc., Vol. 131, Issue (48) ; 12, 2009; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- ENGLISH
Similar Records
Internal And External Factors in the Structural Organization in Cocrystals of the Mixed-Metal Endohedrals (GdSc2N@I(H)-C(80), Gd(2)ScN@I(H)-C(80), And TbSc(2)N@I(H)C(80) ) And Nickel(II) Octaethylporphyrin
A DFT analysis of the ground and charge-transfer excited states of Sc3N@Ih–C80 fullerene coupled with metal-free and zinc-phthalocyanine