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Ternary Alkali Metal Transition Metal Acetylides

The first alkali metal transition metal acetylides of general composition A2M0C2 (A = Na − Cs, M0 = Pd, Pt) were obtained by solid state reactions of alkali metal acetylides with palladium and platinum. They are characterized by chains, which are separated by alkali metal ions. Analogous chains also separated by alkali metal ions are the characteristic structural feature of acetylides of composition AMIC2, which are accessible by reacting AC2H with MII in liquid ammonia (A = Li − Cs, MI = Cu, Ag, Au). Despite their structural similarities they possess different properties, as acetylides of composition A2M0C2 are semiconductors with very small indirect band gaps and slightly extended C–C distances compared to a C–C triple bond, whereas acetylides of composition AMIC2 show a typical salt-like behavior with C–C distances close to the expected value for a C–C triple bond of 120 pm. But with the help of simple chemical models these differences can be made plausible. Furthermore, it is shown that only by a combination of different methods (powder diffraction with X-rays and neutrons, solid state NMR spectroscopy, Raman spectroscopy) it was possible to characterize this new class of compounds structurally and chemically.