The Chemical Nature of Buckminsterfullerene (C ₆₀ ) and the Characterization of a Platinum Derivative

Abstract

Little is known about the chemical nature of the recently isolated carbon clusters (C,,, C,,, C,,, and so forth). One potential application of these materials is as highly dispersed supports for metal catalysts, and therefore the question of how metal atoms bind to C,, is of interest. Reaction of C,, with organometallic ruthenium and platinum reagents has shown that metals can be attached directly to the carbon framework. The native geometry of C,, is almost ideally constructed for dihaptobonding to a transition metal, and an x-ray diffraction analysis of the platinum complex [(C6H5)3P]2Pt(q2-C60)-C4H80 revealed a structure similar to that known for [(C,H,)3P]2Pt(q2-ethylene).The reactivity of C,, is not like that of relatively electron-rich planar aromatic molecules such as benzene. The carbon-carbon double bonds of C,, react like those of very electron-deficient arenes and alkenes.

Raman studies of Pd-C nanocomposites

“…Metal atoms are usually coordinated in the C-C double bond (6 -6 bond) located between two hexagons on the surface of the C 60 molecule. Some of [(PR 3 ) 2 Pd (η 2 -C 60 ) complexes (where R = H, ethylene or phenyl group) were synthesised and theoretically and experimentally analysed and presented in the literature [18][19][20][21]. In addition, organometal polymers with a transition element Pd C 60 , by reaction of fullerene C 60 with a dibenzylideneacetone (DBA) complex of Pd, were prepared as well [22,23].…”

Disorder and the molecular packing of C60buckminsterfullerene: a direct electron-crystallographic analysis

“…For example, accurate bond lengths for the C60 molecule had only been obtained crystallographically from molecular derivatives (Hawkins, Mayer, Lewis, Loren & Hollander, 1991;Fagan, Calabrese & Malone, 1991;Birkett, Hitchcock, Kroto, Taylor & Walton, 1992;Tebbe et al, 1992) until the low-temperature structure was solved (Liu, Lu, Kapes & Ibers, 1991) but similar bond lengths had been obtained previously by nuclear magnetic resonance (NMR) spectral simulation (Johnson, Bethune & Yannoni, 1992). In addition to the lattice perturbations already mentioned, there is yet another possible disorder that could seriously affect the outcome of a crystallographic analysis of the room-temperature form.…”

Free energies, kinetics, and photoelectron-transfer properties, and theoretical and quantitative structural relationship studies of [SWCNT(5,5)-armchair-C n H20][R] (R = η2-C m Pd(dppf), η2-C m Pd(dppr), and η2-C m Pd(dppcym)2, n = 20 to 300 and m = 60 and 70) nanostructure complexes

“…The first metal complexes containing one or several bis (triorganylphosphine)platinum fragments attached to the C 60 core and coordinated in the olefinic η 2 mode were described in 1991 [1][2][3], revealing that fullerenes, at least buckminsterfullerene C 60 , can function as ligands in reactions with transition metals. Electronic structures of exohedral palladium complexes of [60] and [70] fullerenes with diphenylphosphinoferrocenyl, diphenylphosphinoru thenocenyl, and diphenylphosphinocymantrenyl ligands were studied by cyclic voltammetry and semi-empirical quantum chemical calculations in 2004 [1].…”

“…Electronic structures of exohedral palladium complexes of [60] and [70] fullerenes with diphenylphosphinoferrocenyl, diphenylphosphinoru thenocenyl, and diphenylphosphinocymantrenyl ligands were studied by cyclic voltammetry and semi-empirical quantum chemical calculations in 2004 [1]. The probable sites of the electronic changes in these complexes under electrochemical oxidation and reduction have also been determined [1][2][3][4].…”

“…The only exceptions known to date are polymeric homoligand complexes of C 60 with palladium or platinum, which are prepared by the direct reaction of fullerene with zero-valent complexes of these metals with a weakly bound ligand, dibenzylideneacetone [1][2][3][4][5][6][7][8]. The platinum and palladium complexes (C 60 )M x (M = Pt and Pd) can also be prepared from the Pt(0) and Pd cyclooctadiene complexes.…”