The Organometallic Reader

Dedicated to the teaching and learning of modern organometallic chemistry.

Epic Ligand Survey: Metal Alkyls (Part 2)

with 4 comments

In this post, we’ll explore the most common synthetic methods for the synthesis of alkyl complexes. In addition to enumerating the reactions that produce alkyl complexes, this post will also describe strategies for getting around β-hydride elimination when isolable alkyl complexes are the goal. Here we go!

Properties of Stable Alkyl Complexes

Stable alkyl complexes must be resistant to β-hydride elimination. In the last post we identified four key conditions necessary for elimination to occur:

1. The β-carbon must bear a hydrogen.
2. The M–C and C–H bonds must be able to achieve a syn coplanar orientation (pointing in the same direction in parallel planes).
3. The metal must bear 16 total electrons or fewer and possess an open coordination site.
4. The metal must be at least d2.

Stable alkyl complexes must violate at least one of these conditions. For example, titanium(IV) complexes lacking d electrons β-eliminate very slowly. The complex below likely also benefits from chelation (see below).

Without d electrons, elimination becomes difficult.

No d electrons here!

Complexes have been devised that are unable to achieve the syn coplanar orientation required for elimination, or that lack β-hydrogens outright. A few examples are provided below—one has to admire the cleverness of the researchers who devised these complexes. The metallacyclobutane is particularly striking!

Complexes whose beta-C–H bonds cannot align in a syn coplanar manner with the M–C bond.

Complexes whose beta-C–H bonds cannot align in a syn coplanar manner with the M–C bond.

Using tightly binding, chelating ligands or a directing group on the substrate, the formation of 16-electron complexes susceptible to β-hydride elimination can be discouraged. Notice how the hyrdrogen-bonding L2 ligands in the central complex below hold the metal center in a death grip.

Tightly chelating ligands prevent the opening of a coordination site.

Tightly chelating ligands prevent the opening of a coordination site.

Finally, it’s worth noting that complexes with an open coordination site—such as 16-electron, square-planar complexes of Ni, Pd, and Pt important for cross-coupling—are susceptible to reactions with solvent or other species at the open site. Bulky alkyl ligands help prevent these side reactions. In the example below, the methyl groups of the o-tolyl ligands extend into the space above and below the square plane, discouraging the approach of solvent molecules perpendicular to the plane.

The approach of solvent perpendicular to the square plane is slowed by methyl groups on the aryl ligand.

The approach of solvent perpendicular to the square plane is slowed by methyl groups on the aryl ligand.

Many transition metal complexes catalyze (E)/(Z) isomerization and the isomerization of terminal alkenes (α-olefins) to internal isomers via β-hydride elimination. This is a testament to the importance of this process for alkyl complexes. Of course, transient alkyl complexes may appear to be susceptible to β-hydride elimination, but if other processes are faster, elimination will not occur. Thus, the optimization of many reactions involving alkyl complexes as intermediates has involved speeding up other processes at the expense of β-hydride elimination—hydrocyanation is a good example.

Synthesis of Alkyl Complexes

The dominant synthetic methods for alkyl complexes are based on nucleophilic attack, electrophilic attack, oxidative addition, and migratory insertion. The first two methods should be intuitive to the organic chemist; the second two are based on more esoteric (but no less important) reactions of organometallic complexes.

Metals bearing good leaving groups are analogous to organic electrophiles, and are susceptible to nucleophilic attack by organolithiums, Grignard reagents, and other polarized organometallics. These reactions can be viewed as a kind of transmetalation, as the alkyl ligand moves from one metal to another. Electron-withdrawing X-type ligands like –Cl and –Br should jump out as good leaving groups. On the other hand, clean substitution of L-type ligands by anionic nucleophiles is much more rare (anionic complexes would result).

Simple and straightforward: nucleophile attacks electrophilic metal.

Simple and straightforward: nucleophile attacks electrophilic metal.

Many anionic metal complexes are nucleophilic enough to attack electrophilic sources of carbon such as alkyl and acyl halides in an electrophilic attack mode. An available lone pair on the metal and open coordination site are prerequisites for this chemistry. The charge on the complex increases by one unit (in effect, negative charge is transferred to the electrophile’s leaving group). We can classify these as oxidative ligation reactions—notice that the oxidation state of the metal increases by two units.

Oxidative ligation for the synthesis of alkyl complexes. Total electron count does not change.

Oxidative ligation for the synthesis of alkyl complexes. Total electron count does not change.

Oxidative addition results in the cleavage of a W–Z bond and placement of two new X-type ligands (–W and –Z) on the metal center, with an increase in the oxidation state of the metal and the total electron count by two units. Organic halides are extremely common substrates for this reaction, the first step in the mechanism of cross-coupling reactions. The oxidized metal complex containing new alkyl and halide ligands is the final product. Notice that two open coordination sites are required (not necessarily simultaneously), the metal center must be amenable to two-electron oxidation, and the number of total electrons of the complex increases by two. In essence, the electrons of the W–Z bond join the complex’s party. Take note that there are many known mechanisms for oxidative addition! We’ll explore these different mechanisms in detail in a future post.

Oxidative addition, with a representative example, for the synthesis of metal alkyl complexes.

Oxidative addition, with a representative example, for the synthesis of metal alkyl complexes.

Finally, migratory insertion of unsaturated organic compounds is an important method for the synthesis of certain alkyl complexes, and an important step of organometallic reactions that result in addition across π bonds. Migratory insertion is the microscopic reverse of β-hydride elimination. The clever among you may notice that the use of migratory insertion to synthesize alkyl complexes seems inconsistent with our observation that its reverse is ubiquitous for metal alkyls—shouldn’t equilibrium favor the olefin hydride complex? In many cases this is the case; however, there are some notable exceptions. For example, perfluoroalkyl complexes are exceptionally stable (why?), so the insertion of fluoroalkenes is often favored over elimination.

Why does this work? Thank fluorine!

Why does this work? Thank fluorine!

As we noted above, we can still invoke kinetically stable alkyl complexes as intermediates in reactions provided subsequent steps are faster. In the next post, we’ll examine the general classes of reactions in which alkyl complexes find themselves the major players, focusing on the specific mechanistic steps that involve the alkyl complex (reductive elimination, transmetalation, migratory insertion, and [naturally] β-hydride elimination).

Written by Michael Evans

March 5, 2012 at 9:35 am

4 Responses

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  1. […] encourages its reverse: migratory insertion of olefins into M–H. Previously we saw the example of perfluoroalkyl ligands, which possess exceptionally stable M–C bonds. The fundamental idea here—that […]

  2. I recall learning that both CO and phosphines participate in migratory insertion reactions. Since both are present, does the one with more tend to migrate (i.e. in the example, did the phosphine migrate over the carbonyl because there were more of them?)

    AMF

    July 13, 2012 at 3:27 am

    • as I ponder this more, I am thinking that an important factor would be the size and type of the metal, and the type of phosphine…

      AMF

      July 16, 2012 at 12:08 pm

      • Aha, sorry for leaving you hanging on this. You’re right! Migratory insertion of phosphines is hampered by steric factors (they tend to be bulky) and the fact that CO is generally more electrophilic than phosphines. The presence of pi orbitals in CO probably helps it, also. Given the choice between phosphine and CO migratory insertion, my gut would say CO in all but the most bizarre of circumstances. Migratory insertion of phosphines would also produce P(V), which has its fair share of issues…

        mevans

        July 16, 2012 at 12:10 pm


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