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




Li, Zhengrong

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Texas Tech University


The study of the salt elimination reactions of transition metal chlorides with tetracarbonylferrate, tetracarbonylcobaltate and pentacarbonylmanganesate to synthesize xenophilic complexes in which the Type A metal has neutral ligands was carried out. The reduction-oxidation reactions in which electrons were transferred from the pentacarbonyl-manganesate and tetracarbonylferrate anions to the transition metal cations hindered the formation of the metal-metal bond between transition metals. In the reactions of transition metal chlorides with tetracarbonylcobaltate anion no reaction occurred unless tetracarbonylcobaltate anion yielded anionic carbonyl cobalt clusters when the less polar solvents replaced THF (THF = tetrahydrofuran). The exception was that the Group 4 metal chlorides reacted with tetracarbonylcobaltate anion to yield the hydrotetracarbonylcobalt. The introduction of pyrroUdine reduced the oxidation potentials of Group 7, 8 metal cations so that the synthesis of xenophilic complexes was possible.

In the reaction of an equal molar mixtvire of trimethyl and triethyl indium with octacarbonylcobalt that generates ketone, the statistical distribution of ketone products was obtained. The pathways for such reaction are proposed.

The compound Mn2(CO)8(C4H9N)2 (C4H9N = pyrrolidine) has been synthesized by placing Mn2(CO)10 into hexanes containing pyrrolidine. A single crystal X-ray structure determination shows the pyrrolidine molecules attach to the manganese atoms in the equatorial position. The bond length between manganese atoms is 2.9415(7) A, longer than that in Mn2(CO)10 and in diaxial substibuted Mn2(CO)10. This is the first disubstituted Mn2(CO)10 by monodentate nitrogen ligand that has trans-equatorial geometry.



Chlorides, Metal-metal bonds, Oxidation-reduction reaction, Organometallic compounds, Transition metal complexes, Metal complexes, Cations