Synthesis of Metal Complexes with an Open‐Cage Fullerene as the Ligand

Abstract

An open-cage C derivative 9 with anilino, hemiketal, and lactone moieties on the edge of the opening was prepared through a fullerene-mixed peroxide procedure. Key steps include decarbonylation, intramolecular Friedel-Crafts reaction and oxetane ring opening rearrangement. The open-cage compound 9 readily reacts with various metal salts. A nickel complex was obtained by treating 9 with NiCl at r.t. followed by purification on a silica gel column. Single-crystal X-ray diffraction analysis showed that the nickel ion is coordinated to two ligands with an octahedral geometry.

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

“…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. In the present work we report the synthesis of palladium complexes using two types of open-cage fullerenes having 11- and 18-membered orifices, respectively.…”

Copper-Catalyzed Reaction of C60 with Tertiary Amines for the Preparation of Spiro-Linked Methanofullerenes and Fullerenoalkanals

“…On the other hand, the remarkable potential of organofullerenes in materials and biomedical science, electronic devices, and nanotechnology has made organic modification of fullerenes receive more attention. , In this respect, the transition metal-promoted or -catalyzed reaction has represented a powerful tool to functionalize fullerenes including radical reactions, C–H activation, and asymmetric reactions . Over the past few years, Cu­(I/II)-promoted transformation of C 60 has gradually attracted increasing attention. , We have been interested in this field and have developed several new methods for the functionalization of C 60 .…”

Nonclassical Abramov Products Formed on Orifices of Cage‐Opened C60Derivatives

“…Next, we applied the similar reactionc onditions to 9, [26] in which C(2)=O(2) andC (3)=O(3) carbonyl groups in 1 are protected asabis(hemiketal) moiety [27] (Scheme 3). In this reaction, methylene derivative 11 was obtainedi n2%y ield, suggestive of in situd eprotection of 9,f ollowed by the hydrolysis of transiently-formed b-oxo-phosphorus ylide whicha lso gave 10 as am ajor product (64 %) via stepwise deoxygenation reactions.…”

“…In this reaction, methylene derivative 11 was obtainedi n2%y ield, suggestive of in situd eprotection of 9,f ollowed by the hydrolysis of transiently-formed b-oxo-phosphorus ylide whicha lso gave 10 as am ajor product (64 %) via stepwise deoxygenation reactions. [26,28] Interestingly,aparto f9 was transformed into 12 (6 %), 13 (2 %), and 14 (2 %) via phosphite-mediated dehydroxyhydrogenation. [29] To our surprise, ac ompound bearing aPatom directly attached to the C 60 skeleton (15)w as also formed in 5% yield, as evidenced by the 13 Cs ignal at d + 56.1 ppm (J CP 144 Hz).…”