Functionalization of C60 has been achieved by [2+2] photocycloaddition reactions of enones and [2+4] cycloaddition reactions of dienes, the course of these reactions can be followed using electrospray mass spectrometry using a special tagging reagent. Using tagged C60 it was shown that cis and trans cycloadducts are formed from ketones such as 3-methylcyclohexenone. We have also employed the new technique of 3He NMR spectrometry. 3He is an NMR-active nucleus. Fullerenes containing an endohedral 3He atom can be examined by NMR to obtain structural information and potentially determine isomer distributions. Examples, of helium spectra of fullerene hydrides are presented.