The Organometallic Reader

Dedicated to the teaching and learning of modern organometallic chemistry.

Posts Tagged ‘beta-hydride elimination

β-Elimination Reactions

with 7 comments

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.

Comparing organic and organometallic β-eliminations. A nucleophilic bond or lone pair promotes loss or migration of a leaving group.

Comparing organic and organometallic β-eliminations. A nucleophilic bond or lone pair promotes loss or migration of a leaving group.

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.

β-Hydride Elimination

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 »

Migratory Insertion: 1,2-Insertions

with 6 comments

Insertions of π systems into M-X bonds are appealing in the sense that they 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.

1,2-Insertion is dinstinct from nucleophilic/electrophilic attack on coordinated ligands.

1,2-Insertion is dinstinct from nucleophilic/electrophilic attack on coordinated ligands.

Like 1,1-insertions, 1,2-insertions generate a vacant site on the metal, which is usually filled by external ligand. For unsymmetrical alkenes, it’s important to think about site selectivity: which atom of the alkene will end up bound to metal, and which to the other ligand? To make predictions about site selectivity we can appeal to the classic picture of the M–X bond as M+X. Asymmetric, polarized π ligands contain one atom with excess partial charge; this atom hooks up with the complementary atom in the M–R bond during insertion. Resonance is our best friend here!

The site selectivity of 1,2-insertion can be predicted using resonance forms and partial charges.

The site selectivity of 1,2-insertion can be predicted using resonance forms and partial charges.

A nice study by Yu and Spencer illustrates these effects in homogeneous palladium- and rhodium-catalyzed hydrogenation reactions. Unactivated alkenes generally exhibit lower site selectivity than activated ones, although steric differences between the two ends of the double bond can promote selectivity. Read the rest of this entry »

Epic Ligand Survey: Metal Alkyls (Part 3)

leave a comment »

In this last post on alkyl ligands, we’ll explore the major modes of reactivity of metal alkyls. We’ve discussed β-hydride elimination in detail, but other fates of metal alkyls include reductive elimination, transmetallation, and  migratory insertion into the M–C bond. In a similar manner to our studies of other ligands, we’d like to relate the steric and electronic properties of the metal alkyl complex to its propensity to undergo these reactions. This kind of thinking is particularly important when we’re interested in controlling the relative rates and/or extents of two different, competing reaction pathways.

Reactions of Metal Alkyl Complexes

Recall that β-hydride elimination is an extremely common—and sometimes problematic—transformation of metal alkyls. Then again, there are reactions for which β-hydride elimination is desirable, such as the Heck reaction. Structural modifications that strengthen the M–H bond relative to the M–C bond encourage β-hydride elimination; the step can also be driven by trapping of the metal hydride product with a base (the Heck reaction uses this idea).

During the Heck reaction, beta-hydride elimination is driven by a base.

During the Heck reaction, beta-hydride elimination is driven by a base.

On the flip side, stabilization of the M–C bond discourages elimination and 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 electron-withdrawing groups on the alkyl ligand stabilize the M–C bond—is quite general. Hartwig describes an increase in the “ionic character” of the M–C bond upon the addition of electron-withdrawing groups to the alkyl ligand (thereby strengthening the M–C bond, since ionic bonds are stronger than covalent bonds). Bond energies from organic chemistry bear out this idea to an extent; for instance, see the relative BDEs of Me–Me, Me–Ph, and Me–CCH in this reference. I still find this explanation a little “hand-wavy,” but it serves our purpose, I suppose. Read the rest of this entry »

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!

Read the rest of this entry »

Written by Michael Evans

March 5, 2012 at 9:35 am

Epic Ligand Survey: Metal Alkyls (Part 1)

with 3 comments

Epic Ligand Survey: Metal Alkyls (Part 1)With this post we finally reach the defining ligands of organometallic chemistry, alkyls. Metal alkyls feature a metal-carbon σ bond and are usually actor ligands, although some alkyl ligands behave as spectators. Our aim will be to understand the general dependence of the behavior of alkyl ligands on the metal center and the ligand’s substituents. Using this knowledge, we can make meaningful comparisons between related metal alkyl complexes and educated predictions about their likely behavior. Because alkyl ligands are central to organometallic chemistry, I’ve decided to spread this discussion across multiple posts. We’ll deal first with the general properties of metal alkyls.

General Properties

In the Simplifying the Organometallic Complex series, we decomposed the M–C bond into a positively charged metal and negatively charged carbon. This deconstruction procedure is consistent with the relative electronegativities of carbon and the transition metals. It can be very useful for us to imagine metal alkyls essentially as stabilized carbanions—but it’s also important to understand that M–C bonds run the gamut from extremely ionic and salt-like (NaCH3) to essentially covalent ([HgCH3]+). The reactivity of the alkyl ligand is inversely related to the electronegativity of the metal center.

Reactivity decreases as the metal's electronegativity increases.

Reactivity decreases as the metal's electronegativity increases. Values given are Pauling electronegativities.

The hybridization of the carbon atom is also important, and the trend here follows the trend in nucleophilicity as a function of hybridization in organic chemistry. sp-Hybridized ligands are the least nucleophilic, followed by sp2 and sp3 ligands respectively. Read the rest of this entry »

Written by Michael Evans

March 1, 2012 at 12:45 pm

Epic Ligand Survey: Metal Hydrides

with 4 comments

Epic Ligand Survey: Metal HydridesMetal-hydrogen bonds, also known (misleadingly) as metal hydrides, are ubiquitous X-type ligands in organometallic chemistry. There is much more than meets the eye to most M-H bonds: although they’re simple to draw, they vary enormously in polarization and pKa. They may be acidic or hydridic or both, depending on the nature of the metal center and the reaction conditions. In this post, we’ll develop some heuristics for predicting the behavior of M-H bonds and discuss their major modes of reactivity (acidity, radical reactions, migratory insertion, etc.). We’ll also touch on the most widely used synthetic methods to form metal hydrides.

General Properties

Metal hydrides run the gamut from nucleophilic/basic to electrophilic/acidic. Then again, the same can be said of X–H bonds in organic chemistry, which may vary from mildly nucleophilic (consider Hantzsch esters and NADH) to extremely electrophilic (consider triflic acid). As hydrogen is what it is in both cases, it’s clear that the nature of the X fragment—more specifically, the stability of the charged fragments X+ and X—dictate the character of the X–H bond. Compare the four equilibria outlined below—the stabilities of the ions dictate the position of each equilibrium. By now we shouldn’t find it surprising that the highly π-acidic W(CO)5 fragment is good at stabilizing negative charge; for a similar reason, the ZrCp2Cl fragment can stabilize positive charge.*

Metal-hydrogen bonds may be either hydridic (nucleophilic) or acidic (electrophilic). The nature of other ligands and the reaction conditions are keys to making predictions.

Metal-hydrogen bonds may be either hydridic (nucleophilic) or acidic (electrophilic). The nature of other ligands and the reaction conditions are keys to making predictions.

Read the rest of this entry »