title: Theoretical Study of Addition Reactions of L4M(M = Rh, Ir) and L2M(M = Pd, Pt) to Li+@C60.
abstract: The addition reaction of M(Cl)(CO)(PPh3)2(M = Rh, Ir) and M(PPh3)2(M = Pd, Pt) fragments with X@C60(X = 0, Li+) were characterized by density functional theory (DFT) and the artificial force-induced reaction (AFIR) method. The calculated free energy profiles suggested that the η2[6:6]-addition is the most favorable reaction, which is consistent with the experimental observations. In the presence of Li+ion, the reaction is highly exothermic, leading to η2[6:6] product of L4IrLi+@C60. In contrast, an endothermic reaction was observed in the absence of a Li+ion. The encapsulated Li+ion can enhance the thermodynamic stability of the η2[6:6] product. The energy decomposition analysis showed that the interaction between metal fragment and X@C60fragment is the key for the thermodynamic stability. Among the group IA and IIA metal cations, Be2+encapsulation is the best candidate for the development of new fullerene-transition metal complexes, which will be useful for future potential applications such as solar cells, catalysts, and electronic devices.
authors.affiliation: Department of Applied Chemistry, National Chiayi University , Chiayi 60004, Taiwan.|Fukui Institute for Fundamental Chemistry, Kyoto University , Kyoto 606-8103, Japan.
authors.forename: Ming-Chung
authors.initials: MC
authors.lastname: Yang
authors.affiliation: Fukui Institute for Fundamental Chemistry, Kyoto University , Kyoto 606-8103, Japan.
authors.forename: Akhilesh K
authors.initials: AK
authors.lastname: Sharma
authors.affiliation: Fukui Institute for Fundamental Chemistry, Kyoto University , Kyoto 606-8103, Japan.|Department of Chemistry, Faculty of Science, Hokkaido University , North-10 West-8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan.
authors.forename: W M C
authors.identifier: http://orcid.org/0000-0003-0213-0688
authors.initials: WM
authors.lastname: Sameera
authors.affiliation: Fukui Institute for Fundamental Chemistry, Kyoto University , Kyoto 606-8103, Japan.
authors.forename: Keiji
authors.initials: K
authors.lastname: Morokuma
authors.affiliation: Department of Applied Chemistry, National Chiayi University , Chiayi 60004, Taiwan.|Department of Medicinal and Applied Chemistry, Kaohsiung Medical University , Kaohsiung 80708, Taiwan.
authors.forename: Ming-Der
authors.identifier: http://orcid.org/0000-0002-5847-4271
authors.initials: MD
authors.lastname: Su