Theoretical Study of Pt(PR3)2(AlCl3) (R = H, Me, Ph, or Cy) Including an Unsupported Bond between Transition Metal and Non-transition Metal Elements: Geometry, Bond Strength, and Prediction

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2011-08, Vol.115 (30), p.8520-8527
• Main Authors: Tsukamoto, Shinya, Sakaki, Shigeyoshi
• Format: Article
• Language: English
• Subjects: A: Molecular Structure, Quantum Chemistry, General Theory; Binding energy; Boundary element method; Functionals; Mathematical analysis; Molecular structure; Orbitals; Platinum
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp202829w

The molecular structure and the binding energy of Pt(PR3)2(AlCl3) (R = H, Me, Ph, or Cy) were investigated by DFT, MP2 to MP4(SDTQ), and CCSD(T) methods. The optimized structure of Pt(PCy3)2(AlCl3) (Cy = cyclohexyl) by the DFT method with M06-2X and LC-BLYP functionals agrees well with the experimental one. The MP4(SDTQ) and CCSD(T) methods present similar binding energies (BE) of Pt(PH3)2(AlCl3), indicating that these methods provide reliable BE value. The DFT(M06-2X)-calculated BE value is close to the MP4(SDTQ) and CCSD(T)-calculated values, while the other functionals present BE values considerably different from the MP4(SDTQ) and CCSD(T)-calculated values. All computational methods employed here indicate that the BE values of Pt(PMe3)2(AlCl3) and Pt(PPh3)2(AlCl3) are considerably larger than those of the ethylene analogues. The coordinate bond of AlCl3 with Pt(PR3)2 is characterized to be the σ charge transfer (CT) from Pt to AlCl3. This complex has a T-shaped structure unlike the well-known Y-shaped structure of Pt(PMe3)2(C2H4), although both are three-coordinate Pt(0) complex. This T-shaped structure results from important participation of the Pt dσ orbital in the σ-CT; because the Pt dσ orbital energy becomes lower as the P–Pt–P angle decreases, the T-shaped structure is more favorable for the σ-CT than is the Y-shaped structure. [Co(alcn)2(AlCl3)]− (alcn = acetylacetoneiminate) is theoretically predicted here as a good candidate for the metal complex, which has an unsupported M–Al bond because its binding energy is calculated to be much larger than that of Pt(PCy3)2(AlCl3).