om0499153_si_005.cif (59.62 kB)
Download file

Nickel, Palladium, and Platinum Complexes of η5-Cyclopentadienide C60R5 Ligands. Kinetic and Thermodynamic Stabilization Effects of the C60Ph5 Ligand

Download (59.62 kB)
posted on 2004-06-21, 00:00 authored by Yoichiro Kuninobu, Yutaka Matsuo, Motoki Toganoh, Masaya Sawamura, Eiichi Nakamura
The nickel−, palladium−, and platinum−RFCp complexes Ni(η5-RFCp)(η3-allylic) (3b, RFCp = C60R5, R = Me, allylic = methallyl; 4a, R = Ph, allylic = allyl; 4b, R = Ph, allylic = methallyl), Pd(η5-RFCp)(η3-allylic) (7a, R = Me, allylic = allyl; 7b, R = Me, allylic = methallyl; 7c, R = Me, allylic = crotyl; 8a, R = Ph, allylic = allyl; 8b, R = Ph, allylic = methallyl; 8c, R = Ph, allylic = crotyl), and Pt(η5-RFCp)(η3-methallyl) (9, R = Me; 10, R = Ph), were synthesized by transmetalation between K(RFCp) (R = Me, Ph) and [Ni(allylic)Br]2, [Pd(allylic)Cl]2, or [Pt(methallyl)Cl]2 in THF at 25 °C for 10 min. The nickel−PhFCp complexes 4a,b are unusually more stable toward molecular oxygen than the corresponding simple nickel cyclopentadienides and survive in air for many hours at elevated temperature. The crystal structures and the electrochemical properties of the palladium complexes suggest that the unusual stability of the PhFCp complexes is due to the kinetic stabilization effect of the five Ph groups surrounding the metal atom and the thermodynamic stabilization effect of the electron-withdrawing fullerene moiety, hence suggesting new opportunities for the synthesis of otherwise unstable organometallic compounds.