Synthesis of Ferrocene/Hydrofullerene Hybrid and Functionalized Bucky Ferrocenes

Abstract

Hydroferration reaction of [60]fullerene or its derivative with [Fe(C5H5)(CO)2]2 gives regioselectively a ferrocene/hydrofullerene hybrid, which upon treatment with Bu4NOH and an alkyl halide affords the corresponding alkylated bucky ferrocene, again regioselectivity via an anion of the ferrocene.

Bucky ferrocene and ruthenocene: serendipity and discoveries

“…Similarly but now without DHA, the reaction of [Fe(C 5 H 5 )(CO) 2 ] 2 with C 60 (PhCH 2 ) 2 [33] in benzonitrile at 160°C afforded the desired hydroferrated product in 82% yield [13]. The cyclopentadiene liberated from [Fe(C 5 H 5 )(CO) 2 ] 2 acts as the hydrogen source in this reaction.…”

“…In Scheme 3 are illustrated representative structures. The initial synthetic route gave an access only to pentamethylated fullerene derivatives, but recent development allowed us to synthesize pentahydrogenated derivatives [13] from which we can synthesize compounds having functional groups (e.g., imide, ester, etc.) amenable to further chemical transformations.…”

Coordination Modes and Different Hapticities for Fullerene Organometallic Complexes

“…Other successful examples of these systems include: (a) the synthesis of complex Rh(η 5 -C 60 R 5 )(CO) 2 , [47], where the average value of Rh-C(Cp of fullerene) distances are shorter when R=Me, than when R=Ph, 2.26 Å and 2.29 Å, respectively; (b) the synthesis of rhenium-hydrofullerene complexes, (CO) 3 -Re-η 5 -C 60 (H) 3 (PhCH 2 ) 2 (Ph) [48] and the modification of R-groups in M-η 5 -C 60 R 5 (M=Re, Fe) by different alkil groups in order to identify new applications in biology, chemistry and other material sciences [49]; (c). The complex with ruthenium(II) where starting from Ru(η 5 -C 60 R 5 )Cl(CO) 2 , the carbonyl ligands can be cleanly replaced in order to obtain the phosphine and isonitrile complexes, without causing cleavage of the fullerene-metal bond [50].…”

A theoretical study on fullerene‐dizincocene hybrids

“…16 Particularly, Toganoh et al recently synthesized a C 60 -ferrocene hybrid C 60 *-FeCp by treatment of C 60 with Bu 4 NOH and excess alkyl halide, where C 60 * denotes a C 60 (CH 3 ) 5 radical. 17 As in ferrocene, a Fe atom is sandwiched between two cyclopentadienyl rings in the hybrid, thus satisfying the 18-electron rule. Its functional derivatization 18 and polymerization 19 have also been reported.…”