Tris(cyclopentadienyl)cerium and -uranium: Relative basicity, structure, and reactions
Thesis/Dissertation
·
OSTI ID:6067303
The trivalent cerium complexes (RC{sub 5}H{sub 4}){sub 3}Ce{center dot}L have been prepared and structurally characterized in order to study the relative basicity of neutral donor ligands toward (RC{sub 5}H{sub 4}){sub 3}Ce. The relative order of increasing basicity is found to be PMe{sub 3} > pyr > P(OCH{sub 2}){sub 3}CEt > thf {approx} quin > PEt{sub 3} > P(OMe){sub 3} >>> NMe{sub 3}. The steric properties of the metal environment and the steric and electronic properties of the metal environment and the steric and electronic properties of the donor ligand influence complex stability. Solution equilibria measurements and crystallographic analyses support the postulate that M-L {pi}-bonding plays a role in (RC{sub 5}H{sub 4}){sub 3}U{center dot}L compounds and not in (RC{sub 5}H{sub 4}){sub 3}Ce{center dot}L compounds. The uranium metallocene, (MeC{sub 5}H{sub 4}){sub 3}U{center dot}thf, reacts with methyl-lithium at low temperature ({minus}30{degrees}C) in the presence of Me{sub 2}NCH{sub 2}CH{sub 2}NMe{sub 2} (tmed) to form a complex that contains a methyl group that is linearly and symmetrically bridging between two (MeC{sub 5}H{sub 4}){sub 3}U groups, and a MeC{sub 5}H{sub 4} group that is sandwiched between two Li(tmed) fragments.
- Research Organization:
- California Univ., Berkeley, CA (USA)
- OSTI ID:
- 6067303
- Country of Publication:
- United States
- Language:
- English
Similar Records
Tris(cyclopentadienyl)cerium and -uranium: Relative basicity, structure, and reactions
(Li(Me sub 2 NCH sub 2 CH sub 2 NMe sub 2 ) sub 2 )(Li sub 2 (Me sub 2 CH sub 2 NMe sub 2 ) sub 2 -(. eta. -. nu. sup 5 ,. nu. sup 5 -MeC sub 5 H sub 4 ))((. eta. sup 5 -MeC sub 5 H sub 4 ) sub 6 U sub 2 (. mu. -Me)) sub 2 : A compound with symmetrically bridging MeC sub 5 H sub 4 and Me groups
Preparation and synthetic utility of MCl{sub 4} (Me{sub 2}NCH{sub 2}CH{sub 2}NMe{sub 2}){sub 2} where M is uranium or thorium
Technical Report
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Sat Oct 01 00:00:00 EDT 1988
·
OSTI ID:6597490
(Li(Me sub 2 NCH sub 2 CH sub 2 NMe sub 2 ) sub 2 )(Li sub 2 (Me sub 2 CH sub 2 NMe sub 2 ) sub 2 -(. eta. -. nu. sup 5 ,. nu. sup 5 -MeC sub 5 H sub 4 ))((. eta. sup 5 -MeC sub 5 H sub 4 ) sub 6 U sub 2 (. mu. -Me)) sub 2 : A compound with symmetrically bridging MeC sub 5 H sub 4 and Me groups
Journal Article
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Wed Jun 07 00:00:00 EDT 1989
· Journal of the American Chemical Society; (USA)
·
OSTI ID:7073218
Preparation and synthetic utility of MCl{sub 4} (Me{sub 2}NCH{sub 2}CH{sub 2}NMe{sub 2}){sub 2} where M is uranium or thorium
Technical Report
·
Wed Sep 01 00:00:00 EDT 1993
·
OSTI ID:10192518
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400702 -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPLEXES
CERIUM COMPLEXES
CHEMICAL PROPERTIES
CHEMICAL REACTION KINETICS
COMPLEXES
KINETICS
LIGANDS
PH VALUE
RARE EARTH COMPLEXES
REACTION KINETICS
STRUCTURAL CHEMICAL ANALYSIS
URANIUM COMPLEXES
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400702 -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPLEXES
CERIUM COMPLEXES
CHEMICAL PROPERTIES
CHEMICAL REACTION KINETICS
COMPLEXES
KINETICS
LIGANDS
PH VALUE
RARE EARTH COMPLEXES
REACTION KINETICS
STRUCTURAL CHEMICAL ANALYSIS
URANIUM COMPLEXES