Effects of Remote Ligand Substituents on the Structures, Spectroscopic, and Magnetic Properties of Two-Coordinate Transition-Metal Thiolate Complexes

Abstract

On the basis of work with earlier linear two-coordinate metal complexes of the amido [−NAriPr4 and −NAriPr6; AriPr4 = C6H3-2,6(C6H3-2,6-iPr2); AriPr6 = C6H3-2,6(C6H2-2,4,6-iPr3] or aryloxo (−OAriPr4 and −OAriPr6) ligands, it was anticipated that the thiolato ligand −SAriPr4 would also induce linear or near-linear coordination, similar to that in M(SAriPr6)2 (M = Cr, Mn, Fe, Co, and Ni) complexes. However, it was found that the M(SAriPr4)2 (M = Cr, Fe, Co, and Ni) species have highly bent geometries with short metal−ligand interactions, owing to the absence of p-isopropyl groups on the flanking aryl rings due to the larger size of sulfur and consequent steric flexibility of the ligand.