Posts Tagged ‘orbitals’
In this post, we’ll begin to explore the molecular orbital theory of organometallic complexes. Some background in molecular orbital theory will be beneficial; an understanding of organic frontier molecular orbital theory is particularly helpful. Check out Fukui’s Nobel Prize lecture for an introduction to FMO theory. The theories described here try to address how the approach of ligands to a transition metal center modifies the electronics of the metal and ligands. The last post on geometry touched on these ideas a little, but we’ll dig a little deeper here. Notably, we need to address the often forgotten influence of the metal on the ligands—how might a metal modify the reactivity of organic ligands?
Ligand Field Theory
The ligand field theory (LFT) fleshes out the ideas of crystal field theory with molecular orbital theory concepts. It provides a method for understanding M–L bonding and antibonding orbitals; however, it has been strongly disputed by computational studies in favor of valence bond models that incorporate hypervalency. Still, LFT provides a more complete picture of complex bonding than crystal field theory, so we’ll discuss it here. Furthermore, the portions of LFT under dispute have nothing to do with CFT, so “no harm no foul.” Let’s take a look at the molecular orbitals of a hypothetical octahedral MLn complex to begin hashing out LFT.