Ch 10 Lecture 2 Ligand Field Theory.ppt

Ch 10 Lecture 2 Ligand Field Theory Octahedral Complexes History Crystal Field Theory only includes ionic interactions in the solid state MO Theory developed and applied only to non-metal compounds Ligand Field Theory combines both for transition metal coordination compounds MO’s for Oh complexes Donor atom = atom in the ligand with a p-orbital or hybrid orbital directly approaching the metal ion to form a s-bond The dxy, dxz, dyz orbitals are not of correct symmetry to s-bond with ligands The dx2-y2, dz2, px, py, pz, and s orbitals all have correct symmetry for interaction with ligands s s p Use the Group Theory Approach to find Molecular Orbitals The six ligand orbitals generate the group orbitals to combine with metal Atomic Orbitals The reducible representation: G = A1g + T1u + Eg Nondbonding metal orbitals: dxy, dxz, dyz orbitals have T2g symmetry Bonding metal orbitals: s orbital has A1g symmetry; px, py, pz have T1u symmetry, and dx2-y2, dz2, have Eg symmetry The 6 metal AO’s of proper symmetry combine with the six ligand group orbitals 6 bonding MO’s are filled by ligand electron pairs The metal t2g Atomic Orbitals are nonbonding (dxy, dxz, dyz) 6 antibonding orbitals are formed with the same symmetries as the bonding orbitals The 2 eg* antibonding orbitals are the lowest energy antibonding orbitals available The d-electrons from the metal ion will fill in the t2g and eg* MO’s All octahedral metal complexes will have the exact same MO diagram, only the number of d-electrons will change The 6 bonding MO’s, with lowered energy for their electron pairs is what holds the metal complex together The d-electrons in the t2g and eg* MO’s Determine the “Ligand Field” Determine the geometry and many characteristics of the metal complex Orbital Splitting and Electron Spin The energy difference between the t2g and eg* MO’s = Do = “delta octahedral” Strong-Field Ligands = ligands whose orbitals interact strongly with metal ion eg* is rais