A kinetic and thermodynamic study of the complexation of tetra-[mu]-boxylatodirhodium(II) with some selected ligands

dc.contributor.advisorBear, John L.
dc.contributor.committeeMemberWendlandt, Wesley W.
dc.contributor.committeeMemberCox, James R., Jr.
dc.contributor.committeeMemberKimball, Aubrey P.
dc.contributor.committeeMemberGeanangel, Russell A.
dc.creatorDas, Kamalendu
dc.description.abstractThe kinetics and thermodynamics of the formation of 1:1 and 1:2 adducts of Rh[lowered 2](O[lowered 2]CR)[lowered 4], where R = CH[lowered 3], CH[lowered 3]OCH[lowered 2] or CH[lowered 3]CH[lowered 2], and ligands, 5'-AMP, L-histidine, DL-methionine, imidazole and pyridine, have been studied at 25[degrees]C in a phosphate buffer of ionic strength 0.1 and pH 7.40, using temperature-jump and 'entropy titration' techniques. The stability constants, enthalpies, and entropies of reactions indicate that the Rh-L (axial) bonding has some ir-interaction. Thus, rhodium(II) methoxyacetate has been found to form the most stable adduct with pyridine which has the highest ir-acceptor ability of all the ligands studied. The kinetic study indicates that the reactions with the nitrogen donor ligands are describable by Eigen's mechanism. Of the three carboxylates, rhodium(II) propionate has the highest rate of reaction with all of the ligands. The variation of the rate with changing R group in the parent carboxylate has been explained by its desolvating effect on the substrate. DL-methionine shows a large ligand effect which can not be explained by the S[lowered N]1IP mechanism.
dc.description.departmentChemistry, Department of
dc.format.digitalOriginreformatted digital
dc.rightsThis item is protected by copyright but is made available here under a claim of fair use (17 U.S.C. §107) for non-profit research and educational purposes. Users of this work assume the responsibility for determining copyright status prior to reusing, publishing, or reproducing this item for purposes other than what is allowed by fair use or other copyright exemptions. Any reuse of this item in excess of fair use or other copyright exemptions requires express permission of the copyright holder.
dc.titleA kinetic and thermodynamic study of the complexation of tetra-[mu]-boxylatodirhodium(II) with some selected ligands
thesis.degree.collegeCollege of Natural Sciences and Mathematics
thesis.degree.departmentChemistry, Department of
thesis.degree.grantorUniversity of Houston
thesis.degree.nameDoctor of Philosophy


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