Document Type

Thesis - Open Access

Award Date

1986

Degree Name

Master of Science (MS)

Department

Chemistry

First Advisor

Henry Behrke

Abstract

The objective of this study was to investigate the sol vent interactions of trans-trichlorooxobis(triphenylphosphine)rhenium(V) in a continuation of studies into the possible use of organorhenium compounds as homogeneous catalysts. The goal was achieved by using sealed tube reactions under high temperature conditions. The same reactions were also carried out under reflux conditions under dry dinitrogen for comparison purposes. As a result of this work, it was found that trans-trichlorooxobis(triphenylphosphine)rhenium(V) with chloroform produced a variety of products at high temperature in sealed tube reactions. When reagent grade chloroform was used tetrachlorobis(triphenylphosphineoxide)rhenium(IV) and tetrachlorobis(triphenylphosphine)rhenium(IV) were produced. When reagent grade chloroform and excess triphenylphosphine were used bis(methyltriphenylphosphonium)hexachlororhenate(IV) was produced. In the reflux reaction with reagent grade chloroform dichloro(ethoxy)oxobis(triphenylphosphine}rhenium(V) was produced as major product, while in presence of added triphenylphosphine an unidentified product was formed. When dry, ethanol-free chloroform, added tri phenylphosphine and trans-trichlorooxobis(triphenylphosphine)rhenium(V) reacted, three products were produced in the sealed tube reaction. Tentative formulations are suggested but require further work before a positive formulation can be made. Under reflux condition trace amounts of tetrachlorobis(triphenylphosphine)rhenium(IV) and tetrachlorobis(triphenylphosphineoxide)rhenium(IV) were produced. Trans-trichlorooxobis(triphenylphosphine)rhenium(V) with toluene in the sealed tube reaction produced a compound containing coordinated triphenylphosphine and triphenylphosphine oxide, which decomposes upon boiling with methylene chloride, under reflux conditions, a polymeric form of trichlorotriphenylphosphinerhenium(III) was produced. In the sealed tube reaction, with added triphenylphospine a mixture of organic products were formed along with a polymeric form of trichlorotriphenylphosphinerhenium(III). Trans-trichlorooxobis(tr1phenylphosphine)rhenium(V) with dry, pure acetone in the sealed tube reaction produced a coordinated acetone complex along with an unidentified product. Under reflux conditions, a compound containing coordinated triphenylphosphine and triphenylphosphine oxide was produced. Trans-trichlorooxobis(triphenylphosphine)rhenium(V) with · acetone in the sealed tube with added triphenylphosphine produced a polymeric form of trichlorotriphenylphosphinerhenium(III), while there is no reaction under reflux conditions. Trans-trichlorooxobis(triphenylphosphine)rhenium(V) with 2-butanone in the sealed tube reaction produces trichlorotriphenyl phosphineoxiderhenium(III) along with unidentified products. Under reflux conditions, a compound containing coordinated triphenylphosphine and triphenylphosphine oxide is formed. Trans-trichlorooxobis(triphenylphosphine)rhenium(V) with 2-butanone in the sealed tube with added triphenylphosphine produces a polymeric form of trichlorotriphenylphosphinerhenium(III). There is no reaction under reflux conditions. Trans-trichlorooxobis(triphenylphosphine)rhenium(V) with carbon tetrachloride in the sealed tube forms tetrachlorobis(triphenylphosphineoxide)rhenium(IV) but with added triphenylprosphine an unidentified compound is formed along with triphenyl phosphine oxide.

Format

application/pdf

Number of Pages

82

Publisher

South Dakota State University

Rights

No Copyright - United State
http://rightsstatements.org/vocab/NoC-US/1.0/

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