Abstract

In recent years (1980–2016), literature on “direct synthesis” of both coordination and organometallic compounds through interaction of metallic elements with organic substrates (ligands) present in a solid as well as liquid assistant grinding (LAG) phases have been reviewed. The synthesis of organometallic and coordination compounds, particularly heterometallic coordination compounds, remains a challenge for modern chemistry. Spontaneous self-assembly (SSA) is a primary approach that proceeds by broad screening, typically with simple, flexible ligands and available metal salts. The “direct synthesis” (DS) is a class of SSA, but prescribes the use of zero-valent metal(s) as a starting material, and typically forces deprotonation of the protic ligand(s) with the formation of unexpected products. The direct synthesis is successfully applied in preparation of heterometallic complexes. The aim of this review is to provide a broad but digestible overview of direct synthesis, i.e., reaction conducted by grinding solid reactants together with no, or a negligible amount, of solvent. We summarize our experience of complied data in the field of “direct synthesis” of heterorganometallic complexes with respect to the corresponding yields, covering preparative characterization and structural aspects.

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