The aim of this work was to investigate the reactivity of C60 n- and HBC2- towards various arylation, alkylation and hydrogenation agents. These highly reactive intermediates can be considered as molecular model systems for the reductive functionalization of polydisperse carbon nano materials. Within this work, the reaction products, addition patterns and principles of the mechanism of the quenching of the highly reactive hexa-peri-hexabenzocoronides and fullerenides are elucidated for a very broad range of various electrophiles. First of all, in chapter 3.1.2, the reactions of low charged fullerides as K2C60 and K2C70 with arylating, alkylating, hydrogenating and oxidation agents were investigated. By means of HPLC techniques and particularly NMR spectroscopy it was found, that only alkylation with activated bromides such as benzyl bromide and geminal bromides leads to selective functionalization of fullerides. Arylation with highly reactive iodonium- and diazonium salts which are known to obtain the highest degree of functionalization for carbon nanotubides and graphenides, yielded mainly in reoxidized starting material and a mixture of various aryl adducts which were not separable. Dimerisation products such as biphenyls were not detected in larger amounts. Hydrogenation with methanol and water was not successful since methanol could not be reduced by K2C60 and hence did not react at all and water as oxidizing agent stopped at the stage of KC60. In case of alkylation reactions geminal dibromides lead exclusively to 1,2-adducts as shown for tetrabromomethane (15), dibromodiphenylmethane (11) and dibromodiethylmalonate (10) whereas monofunctional electrophiles typically yield 1,4-adducts. The cyclopropanation approach enables an alternative approach to bingel adducts and in case of compound 15 a functional key intermediate on the way to inter carbon allotrope hybrids as shown in figure 4.1. In order to investigate alternative addition patterns several benzyl bromide based tether systems were developed and synthesized. However, it could be successfully shown that these predefined bisfunctional electrophiles did not show any unexpected addition chemistry and exclusively led to 1,4-adducts. Depending on the intramolecular distance between the benzyl bromide groups, either 1,4-cycloaddition of one equivalent electrophile or 1,4-adducts of two equivalents electrophile was observed. By increasing the charge on the fullerene from two to six the reactivity is drastically increasing, however the intermediate K6C60 is absolutely insoluble in common polar organic solvents. Reaction with arylating agents such as diazonium and iodonium salts again led to reoxidized starting material and a mixture of non-separable arylated compounds as proven by mass spectrometry. Attempts to hydrogenate the highly reactive intermediate with methanol failed and resulted only in reoxidized starting material. In the case of alkylation reactions with benzyl bromides, hexyl and ethyl iodides no remarkable selectivity was observed. However, there is an influence of the chain length since hexyl and ethyl iodide lead to different product distributions. The broad product spectrum of highly alkylated fullerene derivatives to reoxidized fullerene gives evidence for multiple redox equilibria while reaction. By using geminal dibromides as oxidizing agents, it was shown that the selectivity could be improved significantly. For dibromodiethylmalonate, several bisadducts – namely the e-, trans- 4-, trans-3- and the trans-2-bisadduct – as well as the e,e,e-trisadduct were formed besides a number of higher adducts and could be successfully isolated and characterized. Moreover, it was shown for the first time that hexa-peri-hexabenzocoronenes could be successfully applied in reductive functionalization sequences. The so far not investigated charged potassium salts with stoichiometry K1HBC and K2HBC were successfully characterized by inert absorption spectroscopy and investigated in terms of their behavior against various electrophiles. Arylation attempts with diazonium and iodonium salts solely led to the reoxidized starting material whereas aryl iodide yielded very low amounts of arylated products. Again, no dimerisation products could be detected in large amounts In contrast to fullerides where hydrogenation with methanol did not obtain functionalized products, low amounts of hydrogenated HBC were isolated for the reaction with methanol. However, the main product in all arylation and hydrogenation attempts was reoxidized starting material. In the case of alkylation reactions, alkyl iodides were found to be suitable functionalization agents where as geminal dibromides and benzyl bromides did not show any alkylated products. The alkylation with hexyl and ethyl iodide was further investigated and it could be successfully demonstrated that out of 136 possible stereoisomers only 1,2- trans- and 1,4-trans-addition is observed at the peripheral benzenoid substructure. This was impressively proven by a combination of advanced 2D NMR techniques, HPLC, mass spectrometry, and absorption spectroscopy. Furthermore, high level calculations of the stability of the anion after the first alkylation indicate that the first addition takes always place at the edge – respectively a methine carbon – of the system. In order to avoid energetically unfavorable quinoide structures the second alkyl addition is always observed in close proximity to the first addition for both – fullerenide and HBCide – systems. In addition, there is evidence that the oxidative functionalization is independend of the peripheral substitution at the edge since tbuHBCide 32 as well as HBCide 47 lead both to two isomers with similar absorption spectra. Furthermore, it was found out that the solubility is a key parameter which strongly influences the homogeneity of the resulting products. For both model systems, the nature and the electron affinity of the respective electrophiles crystallized out to be the crucial parameter which decides if the system is functionalized or oxidatively decharged. Going one step further and transferring these results to a polydisperse material like graphene, this indicates that functionalisation takes only place at the edges or defects and is propargating from there while direct functionalization of the all-benzenoid π-system is energetically disfavored.