A mass spectrometric investigation of the gas phase ion—molecule reactions of fullerene cations and dications with various neutral molecules

Ion–Molecule Reactions in Helium Nanodroplets Doped with C60 and Water Clusters

“…[18] (No reaction has been reported under thermal conditions. [19] In our experiments, C 60 is initially at 0.37 K, but the high exothermicity of charge transfer from He + to C 60 will produce electronically or vibrationally excited C 60 2+ .)…”

“…The small (0.18 eV) binding energy of the water monomer explains why no reaction could be identified in gas-phase collisions between H 2 O and C 60 + . [18,19] The adduct simply desorbs too quickly, even at room temperature. [19] In both neutral and cationic systems, the Mulliken partial charges do not show substantial charge transfer between water and C 60 .…”

Ion–molecule reactions of C60Rh+ with CH3X, C6H5X(X = Cl, Br, I) and CH2I2

“…C,,CH, + has also previously been observed by Cooks' group" and condensed phase c 6 0 derivatives containing one to 24 methyls have also been rep~rted.~' Interestingly, CH,I, is observed to transfer a CH, unit to c 6 0 in its reaction with CsoRh+, reaction (17). Although it requires less energy to abstract CH, from CH21, than from CHJ, 79 kcal/mol versus 94 kcal/mol (Table l), the C-I bond strength in CH,I, is also likely to be low, on the order of that for CH,I.…”

“…Finally, in an effort to make a C-Si bond with c 6 0 , diiodosilane (SiH212) was tested. Unfortunately, C6,SiH2+ via the analogous reaction to reaction (17) was not observed and only C :…”

“…While CH, abstraction from CH31, 94 kcal/mol, is similar to that of CH,Br and CH,Cl at 92 kcal/mol and 90 kcal/mol, respectively, as shown in Table 1, the spread between CH, and CH, formation for CH31 at 39 kcal/mol is the largest. Reaction (17) is analogous to reaction (18) for Cs0La+, only the charge C,,Rh+ -k cH,I, -C&Hz+ + RhI, (17) C6oLa' 4-CHZI, C~O C H , + La12+ (18) remains with the metal due to the low ionization energy of La(5.577 eV)33 versus Rh(7.46 eV), which probably translates into a low ionization energy for LaI, . Figure 2 shows FT-ICR mass spectra that illustrate the observation of C6,CH3+ and C6,CH2+.…”