Synthesis and Chemistry of Zintl-Transition Metal Clusters

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This project in the Inorganic, Bioinorganic and Organometallic Chemistry Program is concerned with cluster compounds containing both transition metals and main group atoms, particularly the so-called Zintl compounds. The synthesis and chemistry of such cluster complexes will be developed to understand the fundamental bonding patterns in these compounds. Of particular interest is the creation of discrete complexes which have similarities to the Zintl cluster anions and related Zintl phases. Classical main group atom-containing transition metal carbonyls will be treated with ligands such as CO, and their reduction chemistry will be explored following routes which have been successful for some known clusters of this type. Efforts will center around the heavy elements, namely Tl, Pb and Bi. Plans include exploration of the direct use of various types of alloys for discrete cluster synthesis, including some of the Zintl phases and main group/transition metal alloys. Reactions of bismuth-iron carbonyl and of thallium-iron carbonyl cluster anions will be examined as sources of high nuclearity substances. Compounds will be characterized by single-crystal X-ray diffraction, magnetic measurements, electron microscopy and NMR, Moessbauer and IR spectroscopies as appropriate. The reactions under investigation in this project have strong implications for solid state chemistry and materials science as well as catalysis.