Exploring the Pt→Ligand Back‐Donation Through the Rotational Barrier of an Acyclic Diaminocarbene

Abstract

AbstractThe importance of the Dewar‐Chatt‐Duncanson model for inorganic chemists cannot be overstated. It provides a simple yet robust framework for understanding metal‐ligand bonding in terms of σ‐donation and π‐back‐donation. Some years ago, a publication (Chem. Eur. J. 2015, 21, 2467) introduced a method to effectively correlate experimental NMR data with back‐donation, using [LAu(ADC)]+/0 complexes (ADC=acyclic diaminocarbene) as case study. Here, we theoretically expand the same method to [L(PH3)(ADC)PtCl]+/0 complexes, to verify whether the method is general and to gain deeper insights into the influence of L on Pt‐ADC bonding, especially in the trans position. Such insights hold potential for guiding rational catalyst design strategies.