The redox properties of the first member of a new family of bridgehead-modified difluoromethylenated homofullerenes, [6,61-open C-60(CF2)H-2, were investigated by means of cyclic voltammetry and ESR spectroelectrochemistry. The half-life time of C-60(CF2)H-2 estimated from the decay of the ESR response exceeds 25.5 min at room temperature which will be crucial for practical applications later on. The high stability of C-60(CF2)H-2 was proven to be attributed to spin density delocalization over the fullerene cage as well as to the higher BDE(C-H) value for C-60(CF2)H-2 (as compared to C60H2). Di- and trianions of C-60(CF2)H-2 are less stable and undergo partial dehydrogenation. A detailed voltammetric investigation of H-transfer processes (induced by radicals, radical-anion species or by a Bronsted bases) in the anionic forms of C-60(CF2)H. (m = 0-2) was performed. It allowed suggesting a general scheme integrating various anionic forms of C-60(CF2)Hmn- (n= 1-3) which was corroborated by DFT calculations as well as by a targeted synthesis of deprotonated C-60(CF2)H-m(n-) and C-60(CF2)(2-) anions from C-60(CF2)H-2 using a Bronsted base. Based on these results, an alternative, non-electrochemical synthetic route to C-60(CF2)H-2 using the Zn/ Cu-couple in water/toluene media was elaborated since similar processes regulate the features of hydrogenation of fullerene derivatives in both cases. (C) 2015 Elsevier Ltd. All rights reserved.