The Organometallic Reader

Dedicated to the teaching and learning of modern organometallic chemistry.

Posts Tagged ‘reaction mechanisms

Let’s Get Together: Associative Ligand Substitution

with one comment

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. Ligand substitution in complexes of this class typically occurs via an associative mechanism, involving approach of the incoming ligand to the complex before departure of the leaving group. If we keep this principle in mind, it seems easy enough to predict when ligand substitution is likely to be associative. But how can we spot an associative mechanism in experimental data, and what are some of the consequences of this mechanism?

The prototypical mechanism of associative ligand substitution.

The prototypical mechanism of associative ligand substitution. The first step is rate-determining.

A typical mechanism for associative ligand substitution is shown above. It should be noted that square pyramidal geometry is also possible for the intermediate, but is less common. Let’s begin with the kinetics of the reaction. Read the rest of this entry »

Ligand Substitution: General Ideas

leave a comment »

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.

Charge is conserved in ligand substitution reactions. Four general types of substitution are shown here.

Charge is conserved in ligand substitution reactions. Four general types of substitution are shown here—note the X-for-L and L-for-X types.

How do we know when a ligand substitution reaction is favorable? The thermodynamics of the reaction depend on the relative strength of the two metal-ligand bonds, and the stability of the departing and incoming ligands (or salt sof the ligand, if they’re X type). It’s often useful to think of X-for-X substitutions like acid-base reactions, with the metal and spectator ligands serving as a “glorified proton.” Like acid-base equilibria in organic chemistry, we look to the relative stability of the two charged species (the free ligands) to draw conclusions. Of course, we don’t necessarily need to rely just on primal thermodynamics to drive ligand substitution reactions. Photochemistry, neighboring-group participation, and other tools can facilitate otherwise difficult substitutions.

Ligand substitution is characterized by a continuum of mechanisms bound by associative (A) and dissociative (D) extremes. At the associative extreme, the incoming ligand first forms a bond to the metal, then the departing ligand takes its lone pair and leaves. At the dissociative extreme, the order of events is opposite—the departing ligand leaves, then the incoming ligand comes in. Associative substitution is common for 16-electron complexes (like d8 complexes of Ni, Pd, and Pt), while dissociative substitution is the norm for 18-electron complexes. Then again, reality is often more complicated than these extremes. In some cases, evidence is available for simultaneous dissociation and association, and this mechanism has been given the name interchange (IA or ID).

Over the next few posts, we’ll explore ligand substitution reactions and mechanisms in detail. We’d like to be able to (a) predict whether a mechanism is likely to be associative or dissociative; (b) propose a reasonable mechanism from given experimental data; and (c) describe the results we’d expect given a particular mechanism. Keep these goals in mind as you learn the theoretical and experimental nuts and bolts of substitution reactions.

Written by Michael Evans

May 11, 2012 at 10:06 pm