Show simple item record

dc.contributor.advisorBergbreiter, David E.
dc.creatorLynch, Thomas .
dc.descriptionTypescript (photocopy).en
dc.description.abstractLithium di-n-butyl(tri-n-butylphosphine)argentate(I) (2) and other organoargentate(I) complexes have been prepared and their mechanism of thermal decomposition studied. Chemical characterization of 2 by reaction first with dibromoethane and then iodine yielded only l-iodobutane, showing that 2 was formed quantitatively. ('13)C and ('31)P NMR spectra of lithium dimethyl(tri-n-butylphosphine)argentate(I) are described which support this conclusion. Dilithium trimethyl(tri-n-butylphosphine)argentate(I) was also identified by ('13)C NMR. Analysis of the products of thermal decomposition of 2 suggests that the observed thermal stabilization of 2 with respect to the rapid thermal decomposition of n-butyl(tri-n-butylphosphine)silver(I) (1) is the result of an altered mechanism for carbon-silver bond cleavage. Lithium di-n-butyl(tri-n-butylphosphine)argentate(I) is proposed to decompose to give products derived from n-butyl radicals and n-butyllithium. The principle thermal decomposition products from 2 were octane (26%), butane (71%) and 1-butane (3%). Crossover experiments in which mixed lithium n-butyl(n-pentyl)argentate(I) was thermally decomposed yielded a statistical distribution of coupled products. Substitution of magnesium bromide for lithium had no effect on the product mixture from these thermal decomposition reactions. Kinetics of decomposition of 2 were first order in 2. Other possible pathways for decomposition of organoargentate(I) complexes are discussed and the suggested mechanism for this thermal decomposition reaction is compared to similar organocopper(I) and organogold(I) chemistry. ...en
dc.format.extentxii, 124 leavesen
dc.rightsThis thesis was part of a retrospective digitization project authorized by the Texas A&M University Libraries. Copyright remains vested with the author(s). It is the user's responsibility to secure permission from the copyright holder(s) for re-use of the work beyond the provision of Fair Use.en
dc.subject.classification1981 Dissertation L987
dc.subject.lcshOrganosilver compoundsen
dc.subject.lcshOrganometallic compoundsen
dc.subject.lcshNuclear magnetic resonanceen
dc.subject.lcshPalladium catalystsen
dc.subject.lcshHeterogeneous catalysisen
dc.subject.lcshDecomposition (Chemistry)en
dc.titleDialkylargentate (I) decompositions and the heterogenization of analogous complexes for catalyst preparationsen
dc.typeThesisen A&M Universityen of Philosophyen D. in Philosophyen
dc.format.digitalOriginreformatted digitalen
dc.publisher.digitalTexas A&M University. Libraries

Files in this item


This item appears in the following Collection(s)

Show simple item record

This item and its contents are restricted. If this is your thesis or dissertation, you can make it open-access. This will allow all visitors to view the contents of the thesis.

Request Open Access