  Buckminsterfullerene C60 has received extensive research interest ever since
its discovery. In addition to its interesting intrinsic properties of
exceptional stability and electron-accepting ability, the broad chemical
tunability by decoration or substitution on the C60-fullerene surface makes it
a fascinating molecule. However, to date there is uncertainty about the binding
location of such decorations on the C60 surface, even for a single adsorbed
metal atom. In this work, we report the gas-phase synthesis of the C60V+
complex and its in-situ characterization by mass spectrometry and in-frared
spectroscopy with the help of quantum chemical calculations and molecular
dynamics simulations. We identify the most probable binding position of a
vanadium cation on C60 above a pentagon center in eta5-fashion, demonstrate a
high thermal stability for this complex, and explore the bonding nature between
C60 and the vanadium cation, reveal-ing that large orbital and electrostatic
interactions lie at the origin of the stability of the eta5-C60V+ complex.
