Substituent Effect Parameters: Extending the Applications to Organometallic Chemistry

Abstract

Typically, metal complexes are constituted of an acceptor metal ion and one or more Iigands containing the donor atoms. Accordingly, the properties of a metal complex are equally dependent on the nature of the metal ion and the ligands. Minute structural variations in the ligand will may result in linear changes in the respective energetic parameters and such linear relationships have paramount importance in organometallic chemistry. The variation in ligands is virtually limitless and substantial because of the extent of organic chemistry available for the modelling of desirable ligands, apart from the variation in metal ions. Anyhow, there is still a need for new parameters for the design and quantification of new ligands which in turn leads to the synthesis of metal complexes with possibly predictable chemical properties. Previous studies have demonstrated that quantum chemically derived molecular electrostatic potential (MESP) parameters can be listed as one of the superior quantifiers in this regard, which can act as an effective ligand electronic parameter. The interaction between the ligand part and metal‐containing part will be crucial in assessing the reactivity of organometallic complexes. Here we are applying MESP based substituent constants derived from substituted benzenes to forecast the interaction energies in (pyr*)W(CO)5, (NHC*)Mo(CO)5 and (η6‐arene*)Cr(CO)3 complexes. Ligands and metal ions are varied in each case for better understanding and transparency.