Posts Tagged ‘oxidation’
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. Almost by definition, metal alkyls contain a nucleophilic bond—the M–C bond! This bond can be so polarized toward carbon, in fact, that it can promote the elimination of some of the world’s worst leaving groups, like –H and –CH3. Unlike the organic case, however, the leaving group is not lost completely in organometallic β-eliminations. As the metal donates electrons, it receives electrons from the departing leaving group. When the reaction is complete, the metal has picked up a new π-bound ligand and exchanged one X-type ligand for another.
In this post, we’ll flesh out the mechanism of β-elimination reactions by looking at the conditions required for their occurrence and their reactivity trends. Many of the trends associated with β-eliminations are the opposite of analogous trends in 1,2-insertion reactions. A future post will address other types of elimination reactions.
The most famous and ubiquitous type of β-elimination is β-hydride elimination, which involves the formation of a π bond and an M–H bond. Metal alkyls that contain β-hydrogens experience rapid elimination of these hydrogens, provided a few other conditions are met. Read the rest of this entry »
Over the years, a variety of “quirky” substitution methods have been developed. All of these have the common goal of facilitating substitution in complexes that would otherwise be inert. It’s an age-old challenge: how can we turn a stable complex into something unstable enough to react? Photochemical excitation, oxidation/reduction, and radical chains all do the job, and have all been well studied. We’ll look at a few examples in this post—remember these methods when simple associative or dissociative substitution won’t get the job done.
Substitution reactions of dative ligands—most famously, CO—may be facilitated by photochemical excitation. Two examples are shown below. The first reaction yields only monosubstituted product without ultraviolet light, even in the presence of a strongly donating phosphine.
All signs point to dissociative mechanisms for these reactions (the starting complexes have 18 total electrons each). Excitation, then, must increase the M–L antibonding character of the complex’s electrons; exactly how this increase in antibonding character happens has been a matter of some debate. Originally, the prevailing explanation was that the LUMO bears M–L antibonding character, and excitation kicks an electron up from the HOMO to the LUMO, encouraging cleavage of the M–L bond. A more recent, more subtle explanation backed by calculations supports the involvement of a metal-to-ligand charge-transfer state along with the “classical” ligand-field excited state.
Imagine a screaming baby without her pacifier—that’s a nice analogy for an odd-electron organometallic complex. Complexes bearing 17 and 19 total electrons are much more reactive toward substitution than their even-electron counterparts. Single-electron oxidation and reduction (“popping out the pacifier,” if you will) can thus be used to efficiently turn on substitution. As you might expect, oxidation and reduction work best on electron-rich and electron-poor complexes, respectively. The Mn complex in the oxidative example below, for instance, includes a strongly donating MeCp group (not shown).