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Nuclear magnetic resonance study of ligand exchange on dioxopentakis(trimethyl phosphate)uranium(VI) ion and its triethyl phosphate analogue

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic50177a031· OSTI ID:5217808
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Ligand exchange processes on UO/sub 2/L/sub 5//sup 2 +/ where L is either trimethyl phosphate (TMP) or triethyl phosphate (TEP) have been studied using /sup 1/H and /sup 31/P NMR techniques, respectively. In CD/sub 2/Cl/sub 2/ diluent the rate law for L exchange is rate = 5k/sub ex/ (UO/sub 2/I/sub 5//sup 2 +/), and the exchange mechanism is considered to be either D or I/sub d/. Typical observed rate parameters are k/sub ex/ (260 K) = 95 +- 6 (32.2 +- 2.7) s/sup -1/, ..delta..H/sup double dagger/ = 6.0 +- 0.3 (10.4 +- 0.4) kcal mol/sup -1/, ..delta..S/sup double dagger/ = - 26.1 +- 2.3 (-11.3 +- 1.4) cal deg/sup -1/ mol/sup -1/ for solutions in which (UO/sub 2/L/sub 5//sup 2 +/) = 0.039 (0.139) M, (L) = 0.198 (0.745) M, and (CD/sub 2/Cl/sub 2/) = 12.18 (11.21) M where in each case the first magnitude refers to the TMP system and that in parentheses refers to the TEP system. From a comparison of ..delta..H/sup double dagger//..delta..S/sup double dagger/ linear free energy relationships it is concluded that the surface charge density at the uranium center seen by the equatorial ligands in UO/sub 2/L/sub 5//sup 2 +/ lies between that on the tervalent aluminum and the divalent first-row transition metal centers in AlL/sub 6//sup 3 +/ and ML/sub 6//sup 2 +/, respectively.
Research Organization:
Univ. of Adelaide
OSTI ID:
5217808
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 16:11; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPLEXES
COMPLEXES
CRYOGENIC FLUIDS
ELEMENTS
ESTERS
FLUIDS
HYDROGEN
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NONMETALS
NUCLEAR MAGNETIC RESONANCE
NUCLEI
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
PHOSPHORIC ACID ESTERS
PHOSPHORUS 31
PHOSPHORUS ISOTOPES
PHYSICAL PROPERTIES
RESONANCE
STABLE ISOTOPES
THERMODYNAMIC PROPERTIES
URANIUM COMPLEXES