Coordination Chemistry of Reactive Homoleptic Acetonitrile Complexes with an Unusual Bulky Alkoxo-Phosphine Ligand

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The aim of this project in the Inorganic, Bioinorganic and Organometallic Chemistry program is to develop the chemistry of complex ions of such metals as platinum and rhodium with non-aqueous solvent molecules as the only ligands. It is expected that the solvent molecules be can displaced easily from the metal, allowing the synthesis of complexes which cannot be prepared in the usual way starting with the metal chlorides. The new compounds which will be synthesized will have potential value as catalysts or as reagents for the synthesis of organic compounds. Complexes with non-aqueous solvent molecules, such as acetonitrile, as ligands will be explored as starting materials for the synthesis of ligand-deficient complexes. The solvent complexes will be obtained from halide complexes by reaction with halide abstraction reagents, such as thallium hexafluoro- phosphate or sodium tetraphenylborate, in the presence of a sigma-donor solvent, such as acetonitrile. Reactions of these solvent complexes with an unusual phosphine, tris(2,4,6-trimethoxyphenyl)phosphine, TMPP, will be explored. Preliminary results indicate that homoleptic complexes with only two TMPP molecules bound to the cation can be obtained, due to the steric bulk of the TMPP ligand. These coordinatively unsaturated kinetic products are expected to exhibit high reactivity, especially with regard to susceptibility of the metal center toward attack by small substrates. Attempts will be made to prepare low-valent transition metal complexes of TMPP, so that these complexes may be used to probe the binding and potential activation of small molecules such as carbon monoxide, carbon dioxide, dinitrogen and dihydrogen.