Preparations and mechanism of hydrolysis of ((8)annulene)actinide compounds. [Uranocene]
The mechanism of hydrolysis for bis(8)annulene actinide and lanthanide complexes has been studied in detail. The uranium complex, uranocene, decomposes with good pseudo-first order kinetics (in uranocene) in 1 M degassed solutions of H/sub 2/O in THF. Decomposition of a series of aryl-substituted uranocenes demonstrates that the hydrolysis rate is dependent on the electronic nature of the substituent (Hammett rho value = 2.1, r/sup 2/ = 0.999), with electron-withdrawing groups increasing the rate. When D/sub 2/O is substituted for H/sub 2/O, kinetic isotope effects of 8 to 14 are found for a variety of substituted uranocenes. These results suggest a pre-equilibrium involving approach of a water molecule to the central metal, followed by rate determining proton transfer to the eight membered ring and rapid decomposition to products. Each of the four protonations of the complex has a significant isotope effect. The product ratio of cyclooctatriene isomers formed in the hydrolysis varies, depending on the central metal of the complex. However, the general mechanism of hydrolysis, established for uranocene, can be extended to the hydrolysis and alcoholysis of all the (8)annulene complexes of the lanthanides and actinides.
- Research Organization:
- Lawrence Berkeley Lab., CA (USA)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 5319654
- Report Number(s):
- LBL-20031; ON: DE85017656
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400302 -- Organic Chemistry-- Isotope Effects-- (-1987)
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPLEXES
ALKENES
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
CYCLOALKENES
DATA
DECOMPOSITION
DEUTERIUM
EXPERIMENTAL DATA
HEAVY WATER
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
HYDROLYSIS
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
LYSIS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
RARE EARTH COMPLEXES
REACTION KINETICS
SOLVOLYSIS
STABLE ISOTOPES
SYNTHESIS
URANIUM COMPLEXES
WATER
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400302 -- Organic Chemistry-- Isotope Effects-- (-1987)
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPLEXES
ALKENES
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
CYCLOALKENES
DATA
DECOMPOSITION
DEUTERIUM
EXPERIMENTAL DATA
HEAVY WATER
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
HYDROLYSIS
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
LYSIS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
RARE EARTH COMPLEXES
REACTION KINETICS
SOLVOLYSIS
STABLE ISOTOPES
SYNTHESIS
URANIUM COMPLEXES
WATER