Coordination complexes caused great fascination among chemists during the nineteenth century, although it wasn’t until the century’s end that Alfred Werner determined the fundamental principles of their structure. A fuller understanding of their structures was developed over the first half of the twentieth century. This understanding developed in stages, with newer theories and models building on previous ones rather than replacing them completely.
Crystal Field Theory
In the early 1930’s, American physicists John Hasbrouck van Vleck and Hans Bethe developed a theoretical treatment of crystalline transition metal compounds that explained their magnetic and optical properties. This treatment did not consider bonding in any way, but it did concern itself with the geometry of ligands, or counterions, around a central metal ion. Electrostatic considerations formed the basis of the theory, with attention to repulsive forces between ligand electrons and \(d\) electrons on the metal ion. The model gave good predictions about the effect of ligand geometry on the electronic structure of the metal ion.
Ligand Field Theory
During the 1950’s, British chemists John Stanley Griffith and Leslie Orgel combined some aspects of crystal field theory with molecular orbital theory to produce a bonding model for coordination complexes. Rather than just considering electrostatic interactions between metal and ligand, this approach used orbital interactions to model the role of covalency in determining the electronic structure of the complex.
Angular Overlap Model
This model is a specific approach to considering how ligand and metal orbitals combine to produce molecular orbitals in a coordination complex. It uses the symmetry and orientation of atomic orbitals to determine what combinations of these orbitals should be considered.
Computational Chemistry
The three "pencil-and-paper models" described above for bonding in coordination complexes have been greatly augmented by the power of modern computational chemistry. Although based on the same principles, computational methods offer a much higher level of quantitative information about electronic energy and allow relatively easy assessment of possible structural features such as coordination geometry. Pioneering methods included extended Hückel theory, originally developed by Roald Hoffman and Robert Burns Woodward to study pericyclic reactions. The method was later adapted by Hoffman and others to investigate inorganic and organometallic complexes. More recently, developments such as density functional theory have greatly facilitated computational work on transition metal systems because of their simplified treatment of many-electron systems. These approaches and others like them allow for the prediction of coordination complex properties through a computer interface.
