Homogeneous catalysts are designed with respect to certain chemistries and require appropriate choices of metal centers and ligands in order to optimize the activity and selectivity for the desired reactions.  Often the nature of metal-ligand equilibria in solution is poorly understood from a thermodynamic perspective, specifically how enthalpy and entropy contribute to the free energy of binding. While well-studied factors such as sterics and electronic properties of ligands do contribute to free energy, subtle aspects such as solvation of free ligand, expulsion of coordinated solvent molecules from the metal center, and desolvation of the incoming ligand can have pronounced effects on metal-ligand binding thermodynamic equilibria.  We utilize Isothermal Titration Calorimetry (ITC) to measure the binding thermodynamics of various mono- and bidentate P and N ligands to PdCl2(solv)2 and provide explanations for the enthalpic and entropic contributions to the free energy of binding for in situ synthesis of organometallic species.

Implications of metal-ligand association thermodynamics in organometallic catalyst synthesis and catalytic cycles

244th National Meeting (2012)

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