Silver(I)-Mediated Modification, Dimerization, and Polymerization of an Open-Cage Fullerene

Abstract

The reactions of the open-cage fullerene, MMK-9, with an open 12-membered ring on its surface and silver(I) salts have been examined. The structure of MMK-9 itself has been determined by single-crystal X-ray diffraction. MMK-9 reacts with silver trifluoroacetate in air to form the dimer, {MMK-9(OCH)Ag(AgOCCF)}. Remarkably, five MeO groups have added to the surface of the open cage in a pattern that surrounds a pentagon immediately adjacent to the opening in the cage. Dioxygen has been implicated as the oxidant in this unusual addition of five groups to the open cage. Two silver ions connected to each other by a short argentophillic interaction reside at the core of the centrosymmetric dimer. The reaction of silver nitrate with MMK-9 yields the crystalline polymer, [{MMK-9(OCH)Ag(AgOCH)}·HO]. This polymer consists of dimeric {MMK-9(OCH)Ag} units that are connected into strands through silver ions, which are chelated by the amine functions of one open cage and bound in η-fashion to a pair of carbon atoms on an adjacent open cage.

Regioselective Radical Reaction of Monometallofullerene Y@C2v(9)-C82 With N-arylbenzamidine Mediated by Silver Carbonate

“…Based on the above experimental results and previous reports about metal-mediated fullerene reactions (He et al, 2013;Aghabali et al, 2016;Chao et al, 2016), a plausible reaction mechanism for this silver carbonate-catalyzed reaction is proposed in Figure 3. At first, N-arylbenzimidamide 1 directly reacts with Ag + , which generates 3, and then a radical species 4 is obtained through homolytic cleavage of the nitrogen silver bond.…”

Exohedral Cuprofullerene: Sequentially Expanding Metal Olefin Up to a C60@Cu24 Rhombicuboctahedron

“…Since the first C 60 -Pt complex (η 2 -C 60 )­Pt­(PPh 3 ) 2 was reported in 1991, numerous exohedral metallo­fullerenes have been explored not only because of the extraordinary binding capabilities of fullerenes for transition metals ( M ) in hapto fashion but also because of their novel properties and potential applications. − Compared with the vast number of exohedral metallo­fullerenes with open-shell metals (group 6–10), − only 12 examples containing closed-shell Cu­(I)/Ag­(I)/Au­(I) (two Cu­(I), , seven Ag­(I), − and three Au­(I) structures , ) have been reported so far, and most of them are assembled from organic fullerene derivatives. On the other hand, various Cu­(I)/Ag­(I)/Au­(I)-olefin complexes, − including tris­(η 2 -ethene)-Cu­(I)/Ag­(I)/Au­(I) cationic complexes, − have been prepared, suggesting high binding abilities of olefin for Cu­(I)/Ag­(I)/Au­(I) atoms.…”

Selective Addition of Palladium on the Rim of Open-Cage Fullerenes To Form Mononuclear and Dinuclear Complexes

“…Studies on the coordination chemistry of open-cage fullerenes are still quite rare. The open-cage fullerene reported by Murata et al formed well-characterized ruthenium and silver complexes as reported by Yeh and Balch, respectively. Recently Gan et al reported a nickel complex of an open-cage fullerene with an amino and an acetylacetone-like moiety on the rim of the orifice.…”