Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium

Abstract

Fullerene C60 reacts with dimagnesium(i) compounds LMgMgL, where L is a monoanionic β-diketiminate ligand, to contact ion complexes [(LMg)nC60], where n is predominantly 2, 4 or 6.

Calcium Hydride Reduction of Polycyclic Aromatic Hydrocarbons

“…Treatment of anthracene by compound 6 also provides two‐electron reduction and the formation of compound 8 . While the electrochemical reduction potentials of 5 and 6 have never been determined, a very recent report of the six electron reduction of C 60 by 6 indicates a reducing capability which is at least in the order of E 0 =−2.9 V (vs. SCE) . Consistent with this upper limit, however, such Mg I species are indefinitely stable in benzene ( E 0 =ca.…”

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

“…As a spherical polyene system, the 30 CC bonds in C 60 provide an incredible possibility to bind 30 metal atoms in a saturated μ 30 -(η 2 ) 30 fashion to complete a C 60 @ M 30 icosi­dodecahedron with 20 vertex-shared M 3 -trigons (Scheme b). Up to now, the highest nuclearity is 6 in the reported exohedral metallo­fullerenes, such as 6:1 products through six η 2 or η 2 /η 5 interactions, − and 2:1 adducts through double (μ 3 -η 2 :η 2 :η 2 ) interactions. , It seems an impassable task to fulfill the saturated fashion using open-shell metals, because these metals show coordination numbers no less than 4, and the bulky steric crowding caused by the multiple auxiliary ligands will prevent more M 3 being coated on the neighbor hexagons and restrict the number of M 3 on the C 60 surface, in spite of numerous examples of (μ 3 -η 2 :η 2 :η 2 )-metallo­fullerenes . Therefore, minimizing the steric crowding surrounding the M 3 , for example, adopting the closed-shell Cu­(I) with low coordination number (no more than 4), and using anionic bridge ligands but not terminal ligands are believed to be effective strategies to achieve a high nuclear metallo­fullerene.…”

Mechanistic insights of anionic ligand exchange and fullerene reduction with magnesium(i) compounds

“…In the molecular structure of 8', six [{Ph 2 P(NDip) 2 }Mg] + cations sit comfortably around the C 60 6framework in an approximately octahedral manner and thus the overall diiminophosphinate ligand size is broadly comparable to that of the smaller βdiketiminate examples (e.g. 3c,d with Ar = Mes, Xyl) 13 when the different ligand shape and Complex 8 shows resonances in 1 H and 13 C{ 1 H} NMR spectra for one ligand environment though signals for isopropyl methyl groups are extremely broadened at room temperature ( Figures S37-39).…”