Heterobimetallic complexes have attracted much interest due to their unique structure, bonding, and chemical reactivity. Examples include di- and tri-(orthophosphino)chloro-element 10–15 and 11–15, as well as bis(pyridine-2-thiolato)dichloro-element 10–14 heterobimetallics (10 = Ni, Pd, Pt; 11 = Au; 14 = Ge, Sn, Pb; 15 = As, Sb, Bi). The reactivity of heterobimetallic complexes is highly tunable through substitution of the main group and transition metals, as well as the neutral ligand bound to the latter. Density functional theory helps explain the relative stability of the heterobimetallic core as well its affinity toward different phosphorous-based ligands (PBu3, PPh3, POPh3). We find that 10–14 heterobimetallic complexes are active catalysts in the Negishi coupling reaction. Additionally, heterobimetallic complexes are convenient single-source precursors for the synthesis of a wide range of binary intermetallics, atomically ordered crystalline compounds containing main group and transition metals. While high-temperature solid-state methods to prepare intermetallic compounds exist, softer synthetic methods can provide key advantages, such as enabling the preparation of metastable phases or of smaller particles with increased surface areas for catalysis. Using Pd2Sn as an example, we demonstrate that nanoparticles made in this way can act as uniquely selective catalysts for the reduction of nitroarenes to azoxyarenes.

Synthesis, catalytic activity, and thermolysis of heterobimetallic complexes containing main group–transition metal bonds

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