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

✍ Scribed by Steven Z. Kan; Young C. Xu; Yong G. Byun; Ben S. Freiser

• Publisher: John Wiley and Sons
• Year: 1995
• Tongue: English
• Weight: 622 KB
• Volume: 30
• Category: Article
• ISSN: 1076-5174
• DOI: 10.1002/jms.1190300608

✦ Synopsis

Abstract

The gas‐phase ion‐molecule chemistry of exohedrally bound C~60~Rh^+^ with CH~3~X, C~6~H~5~X (X = Cl, Br, and I) and CH~2~I~2~ is studied using Fourier transform ion cyclotron resonance mass spectrometry. Reactions with CH~3~I and CH~2~I~2~ yield the buckminsterfullerene derivatives, C~60~CH~3~^+^ and C~60~CH~2~^+^, respectively. Energy resolved collisional activation experiments on these two product ions indicate that the methylene group is more strongly bound to C~60~ than the methyl group. This is consistent with methylene being bound by two carbon‐carbon bonds to C~60~, while methyl is bound by a single carbon‐carbon bond. Unlike CH~3~I, CH~3~Cl and CH~3~Br react with C~60~Rh^+^ in a stepwise fashion to yield C~60~Rh(CH~2~)~n~^+^ (n = 1 − 3). Interestingly, C~60~Rh(CH~2~)~2,3~^+^ are shown to be isomers of C~60~RhX^+^ (X = ethene, propene), possibly with a carbon‐carbon bond formed with C~60~. Products containing more than three CH~2~ moieties were not observed. Reactions of C~60~Rh^+^ with C~6~H~5~X(X = Cl, Br, and I) yield C~60~Rh(C~6~H~4~)~n~^+^ (n = 1, 2), in a stepwise fashion via losses of HX. C~60~Rh(C~6~H~4~)~2~^+^ is unreactive with C~6~H~5~X. Again, indirect evidence for CC bond formation to C~60~ is obtained. Consistent with previous observations on C~60~Fe^+^ C~60~Co^+^, the Rh^+^–C~60~ bond energy is found to fall between those of Rh^+^–propene and Rh^+^–benzene, due to the alkene behavior of C~60~.