Source: Dissertation Abstracts International, Volume: 23-05, page: 1511. / Thesis (Ph.D.)--The Florida State University, 1962.

Source: Dissertation Abstracts International, Volume: 40-06, Section: B, page: 2666. / Thesis (Ph.D.)--The Florida State University, 1979.

For safe disposal of nuclear wastes, it is necessary to improve our understanding on the long-term behavior of long-lived actinides in the environment. With respect to the problems of potential migration of radionuclides from a nuclear waste repository, the oxidation state of the actinide can make a difference of a factor of as much as 250 in the rate of migration of the species through the geologic media. The organic (humic) compounds via the phenolic hydroxyl and the carbonyl groups can be of potential importance in the reduction reactions. To study such behavior, the Np(VI) reduction reactions with kojic acid and with tropolone were investigated at tracer level concentration of Np(VI). / From results on the kinetic studies of these reactions, the NpO(,2)('++) is reduced to the NpO(,2)('+) in a one-electron transfer process with no structural change of the dioxo neptunium species. The rates for both reactions are directly proportional to the total concentrations of Np(VI) ion and of oxidizing organic compounds : i.e., kojic acid or tropolone. However, the hydrogen ion dependence on the rate is inverse first-order for kojic acid and inverse second-order for tropolone. The Np(VI) reduction proceeds from the precursor complex via an activated complex and results in oxidation products from radicals formed in the rate-limiting step. The rate for the formation of Np(V) by kojic acid ( k(,1) = 6.06 (+OR-) 0.30 sec('-1)) is faster than by tropolone ( k(,1) = 2.49 (+OR-) 0.10 sec('-1)). The rate of reduction increases with the pK(,a) values (basicity) of the hydroxyl group in oxidizing organic compounds. / The activation parameters for the Np(VI) reduction with kojic acid and tropolone have the same values within the uncertainties: i.e., (DELTA)H('(NOT=)) = 82.7 (+OR-) 3.4 KJ/mol, (DELTA)S('(NOT=)) = 34 (+OR-) 12 J/mol/deg for kojic acid and (DELTA)H('(NOT=)) = 67.2 (+OR-) 3.4 KJ/mol, (DELTA)S('(NOT=)) = 15 (+OR-) 12 J/mol/deg for tropolone. Therefore, the Np(VI) reduction reaction occurs through the same mechanism in both reactions. / Source: Dissertation Abstracts International, Volume: 48-03, Section: B, page: 0753. / Thesis (Ph.D.)--The Florida State University, 1987.

The objective of this dissertation was to test the hypothesis that constrained ligand environments can influence the stability of aluminum-carbon bonds. The synthesis and characterization of a variety of organo-aluminum complexes of tetradentate Schiff-base ligands with varying degrees of backbone flexibility is presented. The reaction of trialkylaluminum compounds with tetradentate Schiff-base ligands having two replaceable hydrogen atoms (SALEN, SALPN, SALOPHEN, and ACEN) proceeds smoothly to yield complexes of the type Al(L)R, L = Shiff-base ligand. The stability of the aluminum carbon bond in these complexes increases with increasing ligand flexibility and is attributed to kinetic rather than thermodynamic factors. When constraints are released more by replacing the tetradentate ligand with two molecules of bidentate 8-quinolinol, complexes of the desired stoichiometry are unstable and rapidly disproportionate. The complex isolated, Al(8-quinolinol)(C(,2)H(,5))(,2) (,2) was high reactivity and bears little resemblance in its properties to those of the mono-alkyl Schiff-base complexes. The dimeric nature was inferred from ('1)H NMR studies and confirmed by single crystal x-ray structure analyses. In related studies with dialkylzinc compounds, adduct formation was observed with Ni SALEN through the two oxygen atoms of the SALEN ligand. However, this complex is highly reactive to both air and moisture. Additional studies, largely x-ray crystallographic in nature, were used to characterize a heterobridged (mu)-oxo iron-silicon compound as well as the first low-spin (mu)-oxo Fe(III) phthalocyanine complex. / Source: Dissertation Abstracts International, Volume: 48-03, Section: B, page: 0751. / Thesis (Ph.D.)--The Florida State University, 1987.

Source: Dissertation Abstracts International, Volume: 31-11, Section: B, page: 6486. / Thesis (Ph.D.)--The Florida State University, 1970.

Source: Dissertation Abstracts International, Volume: 31-11, Section: B, page: 6486. / Thesis (Ph.D.)--The Florida State University, 1970.

Source: Dissertation Abstracts International, Volume: 30-02, Section: B, page: 0543. / Thesis (Ph.D.)--The Florida State University, 1968.

Source: Dissertation Abstracts International, Volume: 31-05, Section: B, page: 2537. / Thesis (Ph.D.)--The Florida State University, 1970.

Source: Dissertation Abstracts International, Volume: 31-05, Section: B, page: 2543. / Thesis (Ph.D.)--The Florida State University, 1970.

Source: Dissertation Abstracts International, Volume: 29-05, Section: B, page: 1595. / Thesis (Ph.D.)--The Florida State University, 1968.