A new heterobimetallic palladium–[60]fullerene complex with bidentate bis-1,1′-[P]2-ferrocene ligand

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 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.…”

“…However, instead of separate (C 60 ) 2 M molecules, a polymeric chain is formed, which is probably indicative of enhanced reactivity (with respect to ligand-free palladium) of the other fullerene double bonds upon coordination of one bond. If an excess of the M(0) compound is present, the specific content of the metal increases [1][2][3][4][5][6][7][8].…”

“…C 60 molecules are presumably linked by metal atoms into onedimensional chains or two-and three-dimensional frameworks. The palladium (platinum) fullerene polymer reacts heterogeneously with P ligands (tertiary phosphines or tertiary phosphites) in solution to give the C 60 ML 2 complexes, which can also be synthesized by other methods [1][2][3][4][5][6][7][8]. The electrochemical synthesis of the (η 2 -C 60 M(PPh 3 ) 2 (M = Pt, Pd) complexes was performed by reacting the dianion of C 60 2− prepared by electrochemical reduction (at a Pt electrode in a toluene-acetonitrile solution in the presence of Bu 4 NBF 4 as the supporting electrolyte) with the ML 2 Cl 2 complex or with a divalent metal chloride in the presence of triphenylphosphine [1][2][3][4].…”

“…These complexes contain a strongly electron-withdrawing fullerene cage and a metallocene group, which can be either electron releasing (ruthenocene) or electron withdrawing (cymantrene) and is linked with the cage through a bisdiphenylphosphine palladium bridge. The electrochemical pattern is impeded because the bisdiphenylphosphine palladium fragment linking these terminal groups is also redox active [1][2][3][4][5][6][7][8].…”

“…Almost all known complexes of fullerenes with an undisturbed electronic system involve only η 2 coordination, which is typical of an isolated olefinic double bond. The η 2 coordination is probably due to the nonplanar surface geometry, which makes the axes of the pseudo-π-orbitals nonparallel and, thus, hampers their bonding to metal orbitals [1][2][3][4][5][6][7][8].…”