Comprehensive Experimental and Computational Study of η6-Arene Ruthenium(II) and Osmium(II) Complexes Supported by Sulfur Analogues of the β-Diketiminate Ligand

Abstract

In comparison to β-diketiminates, a highly exploited class of N,N-chelating ligands, the corresponding β-thioketoiminates, monothio-substituted analogues, have received only minor attention. β-Thioketoiminates are straightforwardly prepared through treatment of an appropriate β-ketoiminate with Lawesson’s reagent. Employing standard synthetic techniques for η6-arene Ru(II) and Os(II) β-diketiminate complexes, an analogous series of chlorido-metal complexes supported by different sized N-aryl substituted β-thioketoiminate ligands is reported. However, metal ligation of a β-thioketoiminate bearing an electron-withdrawing CF3 group was not possible. The metal–chlorine bond in these complexes is readily activated by various sodium or silver salts of weakly coordinating anions, affording coordinately unsaturated cationic formally 16-electron species. All η6-C6H6 metal β-thioketoiminate complexes were characterized by NMR and in the solid state using single crystal X-ray diffraction techniques. Structural studi...