key term - Associative mechanism

Definition

An associative mechanism is a type of substitution reaction where a new ligand binds to a metal center before the original ligand departs. This process involves a transition state where the metal is simultaneously coordinated to both the incoming and outgoing ligands, leading to an intermediate species. This mechanism is particularly relevant in square planar complexes, where sterics and electronic factors influence the reaction pathway.

5 Must Know Facts For Your Next Test

1. In associative mechanisms, the incoming ligand forms a bond with the metal center before the outgoing ligand leaves, leading to an intermediate species.
2. This mechanism often occurs in square planar complexes due to their steric arrangement, which can favor the simultaneous coordination of two ligands.
3. The rate of substitution can be influenced by the nature of the incoming ligand; stronger field ligands can enhance the rate by stabilizing the transitional state.
4. Associative mechanisms can be differentiated from dissociative mechanisms, where the leaving ligand departs before the new ligand coordinates.
5. Factors such as solvent effects and temperature can also impact the associative process, altering the activation energy and overall reaction kinetics.

Review Questions

• How does an associative mechanism differ from a dissociative mechanism in terms of ligand binding?
  • In an associative mechanism, the incoming ligand binds to the metal center at the same time as the outgoing ligand is still attached, forming a transition state with two ligands coordinated to the metal. In contrast, a dissociative mechanism involves the departure of the leaving ligand first, creating an empty coordination site before the new ligand binds. This key difference in timing impacts how each mechanism proceeds and can affect overall reaction rates.
• Discuss how sterics and electronic factors influence associative mechanisms in square planar complexes.
  • Sterics play a significant role in associative mechanisms because square planar complexes have specific geometric constraints that dictate how ligands approach the metal center. Electronic factors are equally important, as strong field ligands can stabilize the transition state formed during the reaction. The combined effects of these factors determine whether an associative pathway is favored over other mechanisms and influence reaction rates.
• Evaluate how solvent effects might alter the kinetics of substitution reactions involving an associative mechanism in square planar complexes.
  • Solvent effects can significantly influence substitution reactions involving an associative mechanism by altering solvation dynamics and stabilization of the transition state. For example, polar solvents may stabilize charged intermediates or transition states more effectively than non-polar solvents, potentially lowering activation energy and increasing reaction rates. Additionally, solvent interactions with ligands can impact their approach to the metal center, further influencing overall kinetics and favorability of substitution reactions.

Related terms

transitional state: The transitional state is a temporary structure that occurs during a chemical reaction, representing the highest energy point along the reaction pathway where old bonds are breaking and new bonds are forming.

substitution reaction: A substitution reaction involves the replacement of one ligand in a coordination complex with another ligand, resulting in the formation of a new complex.

square planar complex: A square planar complex is a type of coordination compound that has a square arrangement of ligands around a central metal atom, common in transition metal complexes with d8 electron configurations.