A biphasic displacement of [60]fullerene from fac-(dihapto-[60]fullerene)(dihapto-1,10-phenanthroline) tricarbonyl molybdenum (0)

Electrochemistry and [60]fullerene displacement reactions of (dihapto-[60]fullerene) pentacarbonyl metal(0) (M = Cr, Mo, W)

“…Buckminsterfullerene ([60]fullerene or C 60 ) reacts with metal carbonyl complexes to form [60]fullerene-metal carbonyl complexes. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] The dihapto (g 2 ) mode of [60]fullerene-transition metal coordination resembles an olefin-metal bond. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] Although all carbons in [60]fullerene are equivalent, the molecule possesses two distinct types of C-C bonds (ring : ring junctions): the C-C bonds between six-membered rings (6 : 6 junction) and the C-C bonds between six-membered and five-membered rings (6 : 5 junctions).…”

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] The dihapto (g 2 ) mode of [60]fullerene-transition metal coordination resembles an olefin-metal bond. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] Although all carbons in [60]fullerene are equivalent, the molecule possesses two distinct types of C-C bonds (ring : ring junctions): the C-C bonds between six-membered rings (6 : 6 junction) and the C-C bonds between six-membered and five-membered rings (6 : 5 junctions). [20][21][22] The C-C bonds at 6 : 6 junctions are shorter than the C-C bonds at 6 : 5 junctions and behave like olefinic units.…”

“…23,24 Despite the potential of [60]fullerene to bind transition metals in a variety of hapticities, the dihapto (g 2 ) mode of coordination is preferred. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] Higher hapticities in aryl-substituted fullerides have been reported but are scarce. 17- 19 The orbitals on the [60]fullerene spherical and rigid surface are spatially oriented in such a way that hapticities higher than two are not favored.…”

“…31 In addition, the formation of [60]fullerene-metal complexes may be favored by the ability of [60]fullerene to participate in p-back bonding. [1][2][3][4] The [60]fullerene-metal bond dissociation energies have been estimated in (g 2 -C 60 )M(PH 3 ) 2 (M = Ni, Pd, Pt) complexes by density functional calculations. [32][33][34] The preparation and electrochemical studies of some [60]fullerene-substituted metal carbonyl complexes of group 6 have been reported.…”

“…[32][33][34] The preparation and electrochemical studies of some [60]fullerene-substituted metal carbonyl complexes of group 6 have been reported. [1][2][3][4][5][6][7][8][9][10][11] However, to our knowledge, there are not reports on the plausible relation between their reactivities toward [60]fullerene-ligand exchange reactions and their electrochemical profiles.…”