Direct Synthesis of Heterometallic Complexes

Abstract

Heterometallic complexes remain in the focus of research of coordination chemistry. Spontaneous self-assembly remains a primary approach for the preparation of metal coordination compounds. Broad screening is typically realized with simple, flexible ligands, and available metal salts often enable serendipitous formation of fascinating structures and compositions. Direct synthesis of heterometallic complexes is based on a spontaneous self-assembly, in which one of the metals is introduced as a powder (zero-valent state) and oxidized during the synthesis (typically by the aerial dioxygen). Two principal one-pot routes (the salt route and ammonium salt route) have been developed in the framework of direct synthesis to yield heterobi-, heterotrimetallic, and mixed-anion heteropolynuclear coordination compounds based on transition metals with protonic and aprotic ligands. In this chapter, we summarize our experience in the field of direct synthesis of polynuclear heterometallic complexes covering preparative and structural aspects, as well as characterization of the compounds obtained.