Thermochemistry of Pt-fullerene complexes: semiempirical study.

Modified Neglect of Differential Overlap (MNDO) and MNDO/d based semiempirical methods are widely employed to explore structure and thermochemistry of molecular systems. In this work, the AM1/d method has been parametrized for systems containing platinum. The proposed scheme delivers excellent performance for binding energies of Pt complexes with ethylene and large pi conjugated hydrocarbons. The estimated bond energies accurately reproduce the results of MP4(SDQ) calculations and show significant improvement over DFT (B3LYP and M05) data. We apply the AM1/d scheme to explore the structure and thermochemistry of several Pt compounds with C(60) and C(70). The calculated binding energies of bare Pt atoms and [Pt(PH(3))(2)] units to the fullerenes are 75 and 45 kcal/mol, respectively. We find that coordination of a single metal center to C(60) activates the fullerene cage making subsequent coordination of Pt more favorable. The bond energy [C(60)-PtC(60)] is calculated to be 65 kcal/mol. The estimated reaction enthalpies are useful for exploring the stability of Pt(x)C(60) polymer systems and their interaction with phosphines. AM1/d predicts a very low barrier to rotation of the coordinated fullerenes in [Pt(C(60))(2)]. The AM1/d scheme is computationally very efficient and can be employed to obtain fast quantitative estimates for binding energies and structural parameters of Pt complexes with large pi conjugated systems like fullerenes and carbon nanotubes.