Document Type

Dissertation - Open Access

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Degree Name

Doctor of Philosophy (PhD)




Reactions of rhenium(V) chloride with triphenylphosphine, triphenylphosphine oxide, and pyridine were investigated, using various solvents. It was found that both the amount of water present and the age of the rhenium(V) chloride played important roles in determining the products formed. The number and kind of products varied with the solvent used, with the more polar solvents giving mostly or all monomeric species. Rhenium(V) chloride and triphenylphosphine in acetonitrile gave tetrachlorobis (triphenylphosphine)rhenium(IV). Rhenium(V) chloride in anhydrous acetorie reacted with pyridine to give dioxotetrakis( pyridine)rhenium(V) chloride dihydrate. Sources for the oxygen and water in the complex are considered. Nonpolar solvents allowed the formation of strong rhenium-torhenium bonds. Rhenium(V) chloride and triphenylphosphine in benzene gave bis (triphenylphosphonium) nonachlorodirhenate(III-IV) and trichloro(tripheny-lphosphine)rhenium(III). Acetone proved to be an unusual case. Oxotrichlorobis( ttiphenylphos phine)rhenium(V) and tetrachlorobis (triphenylphosphine)- rhenium(IV) were obtained as initial precipitates in varying yields, depending upon reaction conditions. From the mother liquor was obtained 1, l-dimethyl-3-oxobutyltriphenylphosphonium pentachloro. triphenylphos phinerhenate (IV) and a mixture of bis (1 , l-dimethyl- 3-oxobutyl triphenylphos phonium) nonachlorodirhenate (III-IV) and bis(l, l-dimethyl-3-oxobutyltriphenylphosphonium) octachlorodirhenate (III). Independent methods of syntheses of these compounds were devised to verify their identity. Triphenylphosphine oxide and rhenium(V) chloride in acetone gave an unusual hydrogenbonded compound, bis(r-hydrogen-bis (triphenylphosphine oxideV nonachlorodirhenate (III-IV). The reaction of oxotrichlorobis (triphenylphosphine)rhenium(V) with hydrogen chloride in acetone led to the isolation of bis (1, l-dimethyl- 3-oxobutyltriphenylphosphonium) hexachlororhenate(IV). The cation moeity was independently synthesized and isolated as the dihydrogen salt by the reaction of mesityl oxide, hydrogen chloride, and triphenylphosphine. The infrared and nmr spectra of the compounds are discussed. The· infrared spectra of a series of hexachlororhenate(IV) salts were recorded from 350-250 cm-1. The position of the asymmetric rhenium-chlorine stretching mode was found to be dependent upon the counter-ion. Various factors leading to the asymmetric shape of the band peak are discussed. Comparison to literature values are made and conclusions are drawn to explain the differences.

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South Dakota State University