Source: Dissertation Abstracts International, Volume: 40-09, Section: B, page: 4295. / Thesis (Ph.D.)--The Florida State University, 1979.

The rates of reduction of the dioxouranium(VI) ion by 4,4$\sp\prime$-dipropylsulfonate-2,2$\sp\prime$ bipyridinium radical anions (ZV$\sp-$ radicals) were determined in the presence of the synthetic polyelectrolytes polyvinylsulfate (PVS), polyacrylic acid (PAA), and polymaleic acid (PMA) using the pulse radiolysis technique. In aqueous PVS solutions the rates of reduction of U(VI) by ZV$\sp-$ radicals are interpreted to reflect territorial binding of U(VI) in the electrostatic field of PVS. In contrast to these results, rate data obtained in PAA and PMA solutions are consistent with the interpretation of site binding of a portion of U(VI) to the carboxylate groups. The specificity of U(VI) binding to PAA is suggested by kinetic experiments in which substitutionally - inert Ru(NH$\sb3$)$\sb6\sp{3+}$ is reduced by ZV$\sp-$ radicals in PAA solutions. Plausible mechanisms for these reactions are presented. / In addition, kinetic data for the reduction of the dioxoactinide(VI) ions, UO$\sb2\sp{2+}$, NpO$\sb2\sp{2+}$, and PuO$\sb2\sp{2+}$ by ZV$\sp-$ radicals were determined at pH 4.0. The measured rate parameters for the reduction of UO$\sb2\sp{2+}$ and NpO$\sb2\sp{2+}$ are in agreement with those predicted by Marcus theory for outer sphere electron transfer, after allowances are made for diffusion. / Source: Dissertation Abstracts International, Volume: 49-12, Section: B, page: 5300. / Major Professor: Gregory R. Choppin. / Thesis (Ph.D.)--The Florida State University, 1988.

The M(CO)$\sb{\rm 6-x}$(PF$\sb3$)$\sb{\rm x}$ complexes where M is Cr, Mo and W and x is 0 to 6 are known. The reactivity of both isomeric forms of the complexes x = 2 and 3 with $\sp{13}$CO and PF$\sb3$ were studied under purely thermal and under photolytic conditions. The results for the thermal reactions in which the samples were in the gas phase are: for chromium and tungsten (100 and 140$\sp\circ$C respectively) the complexes isomerize exclusively via an intramolecular process as there is no C-13 incorporation and only a steady state equilibrium is attained between the isomers. For the molybdenum complexes (100$\sp\circ$C), the reaction is principally an intermolecular process. When starting with either fac- or mer-Mo(PF$\sb3$)$\sb3$(CO)$\sb3$, the intermediate is rigid; stereoselective C-13 incorporation in the Mo(PF$\sb3$)$\sb2$($\sp{13}$CO)(CO)$\sb3$ produced is observed. When starting with either cis- or trans-Mo (PF$\sb3$)$\sb2$(CO)$\sb4$, it appears that the intermediate (Mo(PF$\sb3$)(CO)$\sb4$) will rearrange to place the vacancy cis to the phosphine. In condensed state thermal reactions, for molybdenum complexes, the products obtained result from $\sp{12}$CO and PF$\sb3$ release which remain trapped in the lattice and are reattached. The degree of C-13 incorporation is reduced due to small amount of sample that is volatilized and the small solubility of CO in the complexes at elevated temperatures. Photolytic reactions of the Cr, Mo and W complexes at 100$\sp\circ$C with $\sp{13}$CO present reveal a large degree of product scrambling. When the samples were photolyzed while dissolved in methylcyclohexane, the reaction speed was reduced but is primarily nonselective. Photolytic reactions either neat or in MeCH with PF$\sb3$ present, yielded highly substituted products (x $>$ 3). Finally, procedures to prepare the fac-Mo (PF$\sb3$)$\sb3$(CO)$\sb3$ / isomer in large relative yields are discussed. These reactions were studied with packed column gas chromatography and infrared spectroscopy. / Source: Dissertation Abstracts International, Volume: 51-04, Section: B, page: 1810. / Major Professor: Ronald J. Clark. / Thesis (Ph.D.)--The Florida State University, 1990.

The complexation of Np(V) with aliphatic (oxalic, malonic, succinic, glutaric, and maleic) and aromatic (phthalic, pyromellitic, hemimellitic, trimellitic, and mellitic) polycarboxylic acids was studied by spectrophotometry at 1 M ionic strength (NaClO$\sb4$) and 23$\sp\circ$C. For the aliphatic systems, the stability of the neptunyl complexes was found to decrease as the carbon chain length of the ligand increased which was attributed to an entropy effect. / In polycarboxylate systems, the stability constant decreased in the order hemimellitate $>$ mellitate $>$ pyromellitate $>$ trimellitate, phthalate. With the exception of hemimellitate, this trend follows the order of decreasing basicity of the ligand. After correction of the stability constant for statistical effects, the stability of the mellitate, pyromellitate, trimellitate, and phthalate complexes were approximately the same. / The unexpected strength of hemimellitate complexation was attributed to an increase in electron density at the binding site from the non-chelating carboxylate group through induction. / The complexation of phthalate, trimellitate and hemimellitate and mellitate were studied as a function of pH. Trimellitate and mellitate were found to form MHL as well as ML complexes while for phthalate and hemimellitate only ML species were observed. / The stability constants of the cation-cation complexes Np(V)-U(VI) and Np(V)-Np(V), measured at 6 M ionic strength (HClO$\sb4$) and 25$\sp\circ$C, were found to be 2.45 $\pm$ 0.05 and 1.41 $\pm$ 0.14, respectively. The change in enthalpy for the Np(V)-U(VI) system as determined by the measurement of the stability constant as function of temperature was $-$14.3 $\pm$ 1.6 kJ/mol. / Source: Dissertation Abstracts International, Volume: 50-07, Section: B, page: 2921. / Major Professor: Gregory R. Choppin. / Thesis (Ph.D.)--The Florida State University, 1989.

Substitution of CO with PF$\sb3$ in the Group VIIB dimetal decacarbonyls has been studied under thermal and photolytic conditions. Substitution via photolysis is faster and results in the production of a greater number of isomers. Under both thermal and photolytic conditions, a maximum of four CO ligands may be replaced with PF$\sb3$ in Mn$\sb2$(CO)$\sb{10}$. At least eight of the carbon monoxides can be replaced in Tc$\sb2$(CO)$\sb{10}$, whereas Re$\sb2$(CO)$\sb{10}$ can be fully substituted with PF$\sb3$. Under thermal conditions the rate of reaction proceeds Tc $\gg$ Re $>$ Mn at 130$\sp\circ$C, while under photolytic conditions Tc $\gg$ Mn $>$ Re. For Mn, the metal-metal bond strength does not vary within experimental error from the parent upon the substitution of a single CO with PF$\sb3$. The mixed-metal decacarbonyls, MnTc(CO)$\sb{10}$, MnRe(CO)$\sb{10}$, and ReTc(CO)$\sb{10}$ were synthesized and their reaction with PF$\sb3$ investigated. The possible mechanisms for substitution are reexamined, based upon the observed products. / Source: Dissertation Abstracts International, Volume: 49-07, Section: B, page: 2638. / Major Professor: Ronald J. Clark. / Thesis (Ph.D.)--The Florida State University, 1988.

Source: Dissertation Abstracts International, Volume: 40-06, Section: B, page: 2665. / Thesis (Ph.D.)--The Florida State University, 1979.

Source: Dissertation Abstracts International, Volume: 32-11, Section: B, page: 6280. / Thesis (Ph.D.)--The Florida State University, 1971.

Source: Dissertation Abstracts International, Volume: 32-12, Section: B, page: 6897. / Thesis (Ph.D.)--The Florida State University, 1971.

Source: Dissertation Abstracts International, Volume: 32-11, Section: B, page: 6282. / Thesis (Ph.D.)--The Florida State University, 1971.

Source: Dissertation Abstracts International, Volume: 32-11, Section: B, page: 6284. / Thesis (Ph.D.)--The Florida State University, 1971.