Coordination_Chemistry 第三讲概要1.ppt

Coordination Chemistry Bonding, including crystal field theory and ligand field theory Basis for Bonding Theories Models for the bonding in transition metal complexes must be consistent with observed behavior. Specific data used include stability (or formation) constants, magnetic susceptibility, and the electronic (UV/Vis) spectra of the complexes. Bonding Approaches Valence Bond theory provides the hybridization for octahedral complexes. For the first row transition metals, the hybridization can be: d2sp3 (using the 3d, 4s and 4p orbitals), or sp3d2 (using the 4s, 4p and 4d orbitals). The valence bond approach isn’t used because it fails to explain the electronic spectra and magnetic moments of most complexes. Crystal Field Theory In crystal field theory, the electron pairs on the ligands are viewed as point negative charges that interact with the d orbitals on the central metal. The nature of the ligand and the tendency toward covalent bonding is ignored. Crystal Field Theory Ligands, viewed as point charges, at the corners of an octahedron affect the various d orbitals differently. Crystal Field Theory Crystal Field Theory The repulsion between ligand lone pairs and the d orbitals on the metal results in a splitting of the energy of the d orbitals. d Orbital Splitting d Orbital Splitting In some texts and articles, the gap in the d orbitals is assigned a value of 10Dq. The upper (eg) set goes up by 6Dq, and the lower set (t2g) goes down by 4Dq. The actual size of the gap varies with the metal and the ligands. d Orbital Splitting The colors exhibited by most transition metal complexes arises from the splitting of the d orbitals. As electrons transition from the lower t2g set to the eg set, light in the visible range is absorbed. d Orbital Splitting The splitting due to the nature of the ligand can be observed and measured using a spectrophotometer. Smaller values of ?o result in colors in the green range. Larger gaps shift the color