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Chemistry of trivalent uranium metallocenes: electron-transfer reactions with carbon disulfide. Formation of ((RC/sub 5/H/sub 4/)/sub 3/U)/sub 2/(. mu. -eta/sup 1/,eta/sup 2/-CS/sub 2/)

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00231a007· OSTI ID:5657992
; ;

The trivalent uranium metallocenes (MeC/sub 5/H/sub 4/)/sub 3/U x THF and (Me/sub 3/SiC/sub 5/H/sub 4/)/sub 3/U react with CS/sub 2/ to form the binuclear U(IV) complexes ((RC/sub 5/H/sub 4/)/sub 3/U)/sub 2/(..mu..-eta/sup 1/,eta/sup 2/-CS/sub 2/) (1, R = Me; 2, R = SiMe/sub 3/). Crystals of 1 are monoclinic, P2/sub 1//n, with a = 14.127 (4) A, b = 14.182 (4) A, c = 8.123 (2) A, and ..beta.. = 92.36 (3)/sup 0/ at 23/sup 0/C; for Z = 2 the calculated density is 2.097 g/cm/sup 3/. The structure was refined by full-matrix least-squares to a conventional R factor of 0.025, for 1402 data with F/sup 2/ > 2 sigma (F/sup 2/). The central carbon atom of the complex is disordered across a center of symmetry. The geometry about the CS/sub 2/ ligand (U-S = 2.973 (3) A and U-C = 2.53 (2) A), as well as NMR and susceptibility data, is consistent with two full one-electron transfers into the CS/sub 2/. There is no measurable magnetic interaction between the paramagnetic ions to 5 K.

Research Organization:
Univ. of California, Berkeley
DOE Contract Number:
AC03-76SF00098
OSTI ID:
5657992
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 25:11; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

050700 -- Nuclear Fuels-- Fuels Production & Properties
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPLEXES
ACTINIDE COMPOUNDS
BOND ANGLE
BOND LENGTHS
CARBON COMPOUNDS
CARBON SULFIDES
CHALCOGENIDES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
DATA
DENSITY
DIENES
DIMENSIONS
EXPERIMENTAL DATA
FURANS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
INFORMATION
LATTICE PARAMETERS
LENGTH
LIGANDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHYSICAL PROPERTIES
POLYENES
SILICON COMPLEXES
SILICON COMPOUNDS
SULFIDES
SULFUR COMPOUNDS
SYNTHESIS
TETRAHYDROFURAN
URANIUM COMPLEXES
URANIUM COMPOUNDS