Ternary and Quaternary Alkali Metal Transition Metal Acetylides
One of our long-term research interests focuses on the synthesis and characterisation of ternary acetylides. Numerous ternary alkali metal transition metal acetylides have been reported by our group for d10 configured metals like Pd(0), Pt(0), Cu+, Ag+ and Au+. All these compounds were only obtained as microcrystalline powders so that X-ray powder diffraction data of high quality were needed to solve and refine their crystal structures unambiguously.
In all these compounds the acetylide anions coordinate end-on to the d10 metal (ion) resulting in a linear coordination and polymeric chains as structural fragment (see Fig. 1).
Ternary Alkali Metal Transition Metal Acetylides A2MC2 with A = Na, K and M = Pd, Pt
S. Hemmersbach, B. Zibrowius, W. Kockelmann, and U. Ruschewitz, Chemistry, A European Journal 2001, 7, 1952-1958.
Novel Ternary Alkali Metal Silver Acetylides MIAgC2 (MI = Li, Na, K, Rb, Cs)
W. Kockelmann und U. Ruschewitz, Angew. Chem. Int. Ed. 1999, 38, 3492-3495.
One aim of our current work is the substitution of these transition metals (ions) by Cd2+ or Zn2+ cations to obtain an e.g. tetrahedral coordination sphere so that the formation of 3D networks is conceivable.
As a strong dependence of the direct bandgap of ternary Pd acetylides A2PdC2 upon the respective A+ cation (A = Na, K, Rb) was observed, we are attempting to synthesize quaternary acetylides of composition A’A’’PdC2 to fine-tune the electronic properties of these compounds.
U. Ruschewitz, Coord. Chem. Rev. 2003, 244, 115-136.
U. Ruschewitz, Z. Anorg. Allg. Chem. 2006, 632, 705-719.
M. Weiß und U. Ruschewitz, Z. Anorg. Allg. Chem. 1997, 623, 1208-1210.
U. Ruschewitz, Z. Anorg. Allg. Chem. 2001 , 627, 1231-1235.
H. Billetter, T. Wallraff, U. Schwarz, R. I. Smith, U. Ruschewitz, Z. Anorg. Allg. Chem. 2010, 636, 1834-1838.
U. Cremer, W. Kockelmann, M. Bertmer, U. Ruschewitz, Solid State Sciences 2002, 4, 247-253.
J. Offermanns, U. Ruschewitz, C. Kneip, Z. Anorg. Allg. Chem. 2000, 626, 649-654.