Complexes of Gold(I), Silver(I), and Copper(I) with Pentaaryl[60]fullerides

Abstract

Gold(I), silver(I), and copper(I) phosphine complexes of 6,9,12,15,18-pentaaryl[60]fullerides 1a and 1b, namely, [(4-MeC(6)H(4))(5)C(60)]Au(PPh(3)) (2a), [(4-t-BuC(6)H(4))(5)C(60)]Au(PPh(3)) (2b), [(4-MeC(6)H(4))(5)C(60)]Ag(PCy(3)) (3a), [(4-t-BuC(6)H(4))(5)C(60)]Ag(PPh(3)) (3b), [(4-t-BuC(6)H(4))(5)C(60)]Ag(PCy(3)) (3c), [(4-MeC(6)H(4))(5)C(60)]Cu(PPh(3)) (4a), and [(4-t-BuC(6)H(4))(5)C(60)]Cu(PPh(3)) (4b), have been synthesized and characterized spectroscopically. All complexes except for 3c were also characterized by single-crystal X-ray diffraction. Several coordination modes between the cyclopentadienyl ring embedded in the fullerene and the metal centers are observed, ranging from η(1) with a slight distortion toward η(3) in the case of gold(I), to η(2)/η(3) for silver(I), and η(5) for copper(I). Silver complexes 3a and 3b are rare examples of crystallographically characterized Ag(I) cyclopentadienyls whose preparation was possible thanks to the steric shielding provided by fullerides 1a and 1b, which stabilizes these complexes. Silver complexes 3a and 3b both display unexpected coordination of the cyclopentadienyl portion of the fulleride anion with Ag(I). DFT calculations on the model systems (H(5)C(60))M(PH(3)) and CpMPH(3) (M = Au, Ag, or Cu) were carried out to probe the geometries and electronic structures of these metal complexes.

Complexation and activation of the bisfulleroid C64H4 with triosmium carbonyl clusters

“…The IR spectrum in the carbonyl region is shown in Fig. 1, which is similar to that recorded for the hydrido dienyl complex (m-H) Os 3 (CO) 9 (m,h 4 -C 8 H 11 ) [30], obtained from thermal reaction of 1,5-cyclooctadiene and Os 3 (CO) 10 (NCMe) 2 . The 1 H NMR spectrum of 2 shows two bridging hydride resonances at À15.11 and À15.82 ppm and two sets of hydrocarbon signals in 6.92e5.81 ppm (Fig.…”

Charged Carbon Nanomaterials: Redox Chemistries of Fullerenes, Carbon Nanotubes, and Graphenes

“…Hence, the reaction of alkyl-fulleride with certain organometallic complexes may form covalent metal-fullerene bonds rather than crystalline metallic nanoparticles. 392 Analogous covalent bonds between metal atoms and the basal plane of SWCNTs or graphene have not yet been identified. The more conventional coordination of metal atoms at oxygen-containing defects is well-established, and recently, covalent metal−graphene edge bonds have been demonstrated, 393 although neither approach requires a CCN precursor.…”

Coordination chemistry on carbon surfaces

“…First example is a silver complex, which From Ref. [488]. Pd PPh 2 Ph 2 P S S [467] Pd PPh 2 Ph 2 P S S [467] Pt PPh 2 Ph 2 P S S [467] Pd PPh 2 Ph 2 P Fe [468] Ir OC Et 3 P H PEt 3 [469] Fe [470] W Ph Ph Ph Ph Ph Ph N [471,472] W Ph Ph…”

“…Like for 5 complexes, the introduction of six R groups in the ␣ sites with respect to the common hexagon of C 60 From Ref. [488].…”