Carta Veronica, Mehr S Hessam M, MacLachlan Mark J
Department of Chemistry , University of British Columbia , 2036 Main Mall , Vancouver , British Columbia V6T 1Z1 , Canada.
Inorg Chem. 2018 Mar 19;57(6):3243-3253. doi: 10.1021/acs.inorgchem.8b00031. Epub 2018 Feb 28.
Ligand exchange at a sterically hindered palladium center was investigated for six different ligands. The palladium atom was coordinated to a tridentate, NNN pincer bis(amido)pyridine macrocycle to produce a square-planar complex, in which an acetonitrile molecule occupies one of the coordination sites. Kinetic studies showed that ligand exchange at the palladium center proceeds through an associative mechanism and, as a consequence, is impeded by the small size of the metallomacrocycle cavity. The ligand-exchange rate on the palladium center between acetonitrile and six different ligands has been investigated and compared to the exchange rate on the corresponding open form. Our results demonstrate that macrocyclization of ligands is a way to modify the rate of guest exchange in a square-planar metal complex.
