《无机化学》课件-124_Chapter-12CoordinationCompounds-lecture4.pptVIP

Chapter 12Coordination CompoundLecture 4 12.5.1 The Central Themes of  Crystal Field Theory This theory was originally devised to explain the color of solids, such as ruby(红宝石), since these solids are crystalline, the theory of the field in these materials was named Crystal Field Theory.12.5 Crystal-Field Theory Crystal field theory is a model of the electronic structure of transition metal complexes that considers how the energies of the d orbitals of a metal ion are affected by the electric field of the ligands. Its central themes are:The model assumes that a complex ion forms as a result of electrostatic attractions between the metal cation and the negative charge of the ligands. This negative charge is either partial in a polar neutral ligand like NH3 or full in an anionic ligand like Cl-. 2. According to this theory, the ligands in a  transition metal complex are treated as  negative point charges. In the electric field  of these negative charges, the five d orbitals  of the metal atom no longer have exactly  the same energy. They split into two sets,  with the d orbitals directed toward ligands  having higher energy than those directed  between the ligands.3. The splitting of d-orbital energies minimizes  the overall energy of the system. Thus, the  complex metal ion is lower in energy than  the separated metal ion and ligands. Crystal-Field Theory? Crystal field theory describes bonding in transition metal complexes.? The formation of a complex is a Lewis acid-base reaction.? Both electrons in the bond come from the ligand and are donated into an empty, hybridized orbital on the metal.? Charge is donated from the ligand to the metal.? Assumption in crystal field theory: the interaction between ligand and metal is electrostatic.? The more directly the ligand attacks the metal orbital, the higher the energy of the d orbital. 12.5.2 Splitting of d Orbitals in an  Octahedra