The complexes of cobalt(II) tetraphenylporphyrin ( Co II TPP ) with fullerenes C 60, C 70 and C 60( CN )2 are presented. It is shown that Co II TPP forms complexes with fullerenes in different solvents: [ Co II TPP •fullerene•solvent] ( solvent = C 6 H 6, C 6 H 5 Me , C 6 H 4 Cl 2, CS 2, CHCl 3). The use of additional donors ( Cp 2 Fe , Cr 0( C 6 H 6)2, and TDAE ) in the synthesis of Co II TPP /fullerene complexes allows one to obtain multi-component complexes ranging from neutral [( Co II TPP • Py )2• Cp 2 Fe • fullerene • solvent ] to ionic [ Co II TPP •( D 2•+)•( fullerene •−)• solvent ] ( D 2 = Cr I( C 6 H 6)2, TDAE ). The interaction of Co II TPP with neutral and negatively charged fullerenes is considered. The neutral Co II TPP /fullerene complexes are characterized by a secondary M…C(fullerene) bonding with the shortest Co … C contacts in the 2.69-2.82 Å range and noticeable changes in the electronic structure of the parent components. At the same time, σ-bonding is observed in ionic complexes between Co II TPP and fullerene radical anions with the shortened Co … C contacts being in the 2.28-2.32 Å range. The resulting ( Co II TPP •fullerene−) anions are diamagnetic. The σ-bonding is relatively weak and the ( Co II TPP •fullerene−) anions begin to dissociate above 200 K.
