The Organometallic Reader

Dedicated to the teaching and learning of modern organometallic chemistry.

Posts Tagged ‘fluxionality

Dissociative Ligand Substitution

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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. For the remainder of this post, we’ll focus on the kinetics of the reaction and the nature of the unsaturated intermediate (which influences the stereochemistry of the reaction). The reverse of the first step, re-coordination of the departing ligand (rate constant k–1), is often competitive with dissociation.

A general scheme for dissociative ligand substitution.

A general scheme for dissociative ligand substitution. There’s more to the intermediate than meets the eye!

Reaction Kinetics

Let’s begin with the general situation in which k1 and k–1 are similar in magnitude. Since k1 is rate limiting, k2 is assumed to be much larger than k1 and k–1. Most importantly, we need to assume that variation in the concentration of the unsaturated intermediate is essentially zero. This is called the steady state approximation, and it allows us to set up an equation that relates reaction rate to observable concentrations Hold onto that for a second; first, we can use step 2 to establish a preliminary rate expression.

(1)     rate = k2[LnM–◊][Li]

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Let’s Get Together: Associative Ligand Substitution

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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 »