Toward force fields for atomistic simulations of iridium-containing complexes

The structural and energetic characterization of metal complexes is important in catalysis and photochemical applications. Unraveling their modes-of-action can be greatly assisted by computation, which typically is restricted to computationally demanding methods including electronic structure calculations with density functional theory. Here, we present an empirical force field based on valence bond theory applicable to a range of octahedral Ir(III) complexes with different coordinating ligands, including iridium complexes with a chiral P,N ligand. Using an approach applicable to metal-containing complexes in general, it is shown that with one common parametrization 85% of the 116 diastereomers-all within 21 kcal/mol of the lowest energy conformation of each series-can be correctly ranked. For neutral complexes, all diastereomers are ranked correctly. This helps to identify the most relevant diastereomers which, if necessary, can be further investigated by more demanding computational methods. Furthermore, if one specific complex is considered, the root mean square deviation between reference data from electronic structure calculations and the force field is ≈1  kcal/mol . This, together with the possibility to carry out explicit simulations in solution paves the way for an atomistic understanding of iridium-containing complexes in catalysis.