Investigation of alkylindium-metal carbonyl reaction and synthesis of xenophilic compounds

Xenophilic ("stranger-loving") metal clusters have attracted some attention because they contain two different types of metal centers attached via an unsupported metal-metal bond in which the Type A metal center is coordinated with ligands that only have sigma-donor ability and the Type B metal center is bonded to pi-accepter ligands. Xenophilic compounds have unusual magnetic properties when the Type A metal center has unpaired d-electrons. Only six such clusters and four related compounds have been synthesized so far. This dissertation describes attempts to synthesize xenophilic metal complexes in which the Type A metal has neutral ligands with sigma-donor ability via salt elimination reactions, and the "disportionation" reactions of neutral metal carbonyls in polar or nonpolar solvents in the presence of pyrrolidine. For the salt elimination reactions in which transition metal chlorides reacted with pentacarbonylmanganate and tetracarbonylferrate alkali metal salts, electron transfer from the carbonyl anion to the transition metal cations advanced the formation of metal-metal bonds between the transition metals by electrostatic attraction. With the exception of Group 4 metal chlorides, no reactions were observed between transition metal chlorides and tetracarbonylcobaltate anion. The tetracarbonylcobaltate anion yielded anionic cobalt carbonyl clusters when tetrahydrofuran was replaced by less polar solvents. The introduction of pyrrolidine greatly delayed the oxidation-reduction between Group 7 and 8 metal cations and the pentacarbonylmanganate and tetracarbonylferrate anions, so that the synthesis of xenophilic complexes was possible. Mn2(CO) 8(C4H9N)2 was synthesized and characterized when decacarbonyldimaganese reacted with pyrrolidine in hexanes.;Previous research in our research group showed that ketones are produced when alkylindium compounds react with metal carbonyls under atmospheric pressure of nitrogen. Reactions in which two trialkylindium reacted simultaneously with dicobalt octacarbonyl were carried out in a mechanistic study to examine of the distribution of ketone products. Pathways for this reaction are proposed.