Studies of the Mechanisms of Reactions of Binary Metal Carbonyls

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A kinetic study of the reactions of Group VI-B hexacarbonyls with primary amine and halide ligands was undertaken in order to determine the possible mechanisms of these reactions. As well as the expected dissociative pathway, the reactions with the primary amines were seen to proceed by a concurrent pathway which was dependent upon the ligand concentration. Since nitrogen donor ligands are expected to be poor donor ligands, the mechanism proposed was a "dissociative interchange" mechanism which should not be too dependent upon the nucleophilicity of the ligand. Comparison of the rate constants for the amines studied as well as those ... continued below

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vii, 115 leaves : ill.

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Pardue, Jerry E. May 1977.

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  • Pardue, Jerry E.

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A kinetic study of the reactions of Group VI-B hexacarbonyls with primary amine and halide ligands was undertaken in order to determine the possible mechanisms of these reactions. As well as the expected dissociative pathway, the reactions with the primary amines were seen to proceed by a concurrent pathway which was dependent upon the ligand concentration. Since nitrogen donor ligands are expected to be poor donor ligands, the mechanism proposed was a "dissociative interchange" mechanism which should not be too dependent upon the nucleophilicity of the ligand. Comparison of the rate constants for the amines studied as well as those of the previously investigated Lewis base ligands indicated all such reactions may proceed through the same mechanism. The similarity in rate constants for the ligand-independent and ligand-dependent pathways supports this mechanism. The rate of formation of the final product was seen to be dependent upon the square of the mercuric halide concentration. Therefore, the conversion of Fe(CO)4(HgX)2 to the final product was proposed to proceed by the successive abstraction by each HgX group of two molecules of mercuric halide. These oxidative elimination reactions are related to a chemical model for the intermediate step in the reduction of dinitrogen to ammonia and their similarities and differences are discussed.

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vii, 115 leaves : ill.

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  • May 1977

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  • Aug. 22, 2014, 6 p.m.

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  • Dec. 11, 2018, 1:12 p.m.

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Pardue, Jerry E. Studies of the Mechanisms of Reactions of Binary Metal Carbonyls, dissertation, May 1977; Denton, Texas. (digital.library.unt.edu/ark:/67531/metadc332386/: accessed December 12, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; .