Abstract
The geometrical structures of six square-planar diacetylplatinum(II) complexes ([Pt(Ac)2L], L = hydrazine-type ligand) were calculated using six (B3LYP, CAM-B3LYP, B3PW91, M06, M06HF and PBE) DFT methods and one post-Hartree–Fock (MP2) method combined with 6-31G(d,p) basis sets for nonmetal atoms and LANL2DZ for Pt. Using percent relative errors, M06HF and MP2 are best for predicting Pt–N bond distances, but worst for Pt–C bond distances, whereas B3PW91 is best. Pt–N(pyridine) bonds have higher electron density at the bond critical points than Pt–N(hydrazone) bonds, and the former are more covalent than the latter. Further, Pt–C bonds trans to hydrazone moieties are more covalent than Pt–C bonds trans to Pt–N(pyridine) bonds. Pt–C bonds are mainly due to Pt→Ac back donation rather than Ac→Pt donation; σ-bonding is less important in this case, consistent with the high π-acidity and strong trans effect of acetyl groups. In contrast, Pt→N back donation is negligible and Pt–N bonds are mainly due to N→Pt σ-donation, which stabilizes trans Pt–C bonds.
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