Date of Award

5-1-1974

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

Abstract

Structures are assigned to the six stereoisomers of the complex 2 , 4-pentanedionatobis(S-alaninato)cobalt(III) and to the diastereomers of bis(2, 4-pentanedionato)S-aminoacidatocobalt(III), where the S-amino acid is S-alanine, S-valine, N-methyl-S-alanine and N-methyl-S-valine. Adsorption column chromatography on alumina was used to separate these neutral complexes which are soluble in water and non-aqueous solvents. Electronic absorption spectra are interpreted in assigning geometric isomers and C-O bond anisotropic deshielding arguments are applied to proton nmr chemical shifts in making chiral assignments of the helical diastereomers. A comparison is made between C-O bond deshielding and N-D steric compression. The proton nmr assignments are shown to be independent of the solvent used in measuring chemical shifts and agree with assignments made from circular dichroism spectra in every case. No stereospecificity was observed in these systems or for the complexes bis(2 , 4-pentanedionato)aminoacidato- cobalt(III) where the amino acid is sarcosine, S-proline and S-serine. A convenient, high yield synthesis of tris(2 ,4-pentanedionato)-rhodium(III) is reported.

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