You are not expected to know kinetics for 2330, so skim over these parts. These sections are written from an organometallic chemistry perspective in which all of the electrons from the metal (the d electrons) and those donated by the ligand are counted. Many organometallic complexes have 18 electrons although it is common to have less.
Ligand substitution is the first reaction one typically encounters in an organometallic chemistry course. In general, ligand substitution involves the exchange of one ligand for another, with no change in oxidation state at the metal center. The incoming and outgoing ligands may be L- or X-type, but the charge of the complex changes if the ligand type changes. Keep charge conservation in mind when writing out ligand substitutions.
Despite the sanctity of the 18-electron rule to many students of organometallic chemistry, a wide variety of stable complexes possess fewer than 18 total electrons at the metal center. Perhaps the most famous examples of these complexes are 14- and 16-electron complexes of group 10 metals involved in cross-coupling reactions.
Associative substitution is unlikely for saturated, 18-electron complexes—coordination of another ligand would produce a 20-electron intermediate. For 18-electron complexes, dissociative substitution mechanisms involving 16-electron intermediates are more likely. In a slow step with positive entropy of activation, the departing ligand leaves, generating a coordinatively unsaturated intermediate. The incoming ligand then enters the coordination sphere of the metal to generate the product.
The trans effect is an ancient but venerable observation. First noted by Chernyaev in 1926, the trans effect and its conceptual siblings (the trans influence, cis influence, and cis effect) are easy enough to comprehend. That is, it’s simple enough to know what they are. To understand why they are, on the other hand, is much more difficult.
How important are oxidative additions of non-polar reagents? Very. The addition of dihydrogen (H2) is an important step in catalytic hydrogenation reactions. Organometallic C–H activations depend on oxidative additions of C–H bonds. In a fundamental sense, oxidative additions of non-polar organic compounds are commonly used to establish critical metal-carbon bonds.
Reductive elimination is the microscopic reverse of oxidative addition. It is literally oxidative addition run in reverse—oxidative addition backwards in time! My favorite analogy for microscopic reversibility is the video game Braid, in which “resurrection is the microscopic reverse of death.” The player can reverse time to “undo” death; viewed from the forward direction, “undoing death” is better called “resurrection.”
Insertions of π systems into M-X bonds establish two new σ bonds in one step, in a stereocontrolled manner. As we saw in the last post, however, we should take care to distinguish these fully intramolecular migratory insertions from intermolecular attack of a nucleophile or electrophile on a coordinated π-system ligand. The reverse reaction of migratory insertion, β-elimination, is not the same as the reverse of nucleophilic or electrophilic attack on a coordinated π system.
In organic chemistry class, one learns that elimination reactions involve the cleavage of a σ bond and formation of a π bond. A nucleophilic pair of electrons (either from another bond or a lone pair) heads into a new π bond as a leaving group departs. This process is called β-elimination because the bond β to the nucleophilic pair of electrons breaks. Transition metal complexes can participate in their own version of β-elimination, and metal alkyl complexes famously do so.
