Early actinide alkoxide chemistry. Synthesis, characterization, and molecular structures of Th(IV) and U(IV) aryloxide complexes

Journal Article · Wed Dec 30 00:00:00 EST 1992 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00053a017· OSTI ID:7369111

Berg, J M; Clark, D L; Morris, D E; Sattelberger, A P; Sluys, W.G. Van Der; Watkin, J G ^[1]; Huffman, J C; Steib, W E ^[2]

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1. Los Alamos National Lab., NM (United States)
2. Indiana Univ., Bloomington (United States)

Several synthetic procedures have been developed for the preparation of early actinide aryloxide complexes. Simple alcoholysis of the actinide metallacycle [l brace][(Me[sub 3]Si)[sub 2]N][sub 2][ovr An(CH[sub 2]SiMe[sub 2]N]SiMe[sub 3])[r brace] [An = Th (1), U (2)] using 1 equiv of 2,6-disubstituted phenol results in the protonation of the An-C bond to form mono(aryloxide) complexes An(O-2,6-R[sub 2]C[sub 6]H[sub 3])[N(SiMe[sub 3])[sub 2]][sub 3] [An = U; R = t-Bu (3), i-Pr (4). An = Th; R = t-Bu (5), Me (6)] in essentially quantitative yield. For An = Th, further stepwise substitution products, the bis(aryloxide) or tris(aryloxide) complexes Th(O-2,6-t-Bu[sub 2]C[sub 6]H[sub 3])[sub 2][N(SiMe[sub 3])[sub 2]][sub 2] (7) and Th(O-2,6-t-Bu[sub 2]C[sub 6]H[sub 3])[sub 3][N(SiMe[sub 3])[sub 2]] (8), are readily isolated depending on the stoichiometry of added phenol. Prolonged (36 h) reflux with excess 2,6-di-tert-butylphenol fails to provide the homoleptic Th(O-2,6-t-Bu[sub 2]C[sub 6]H[sub 3])[sub 4] via this simple protonolysis reaction. Thorium metallacycle 1 reacts with 4 equiv of HO-4-t-BuC[sub 6]H[sub 4] to produce polymeric [Th(O-4-t-BuC[sub 6]H[sub 4])[sub 4]][sub x], addition of pyridine to which yields the monomeric adduct Th(O-4-t-BuC[sub 6]H[sub 4])[sub 4](py)[sub 3] (10). For alcoholysis reactions employing the uranium metallacycle (2), addition of slightly greater than 4 equiv of HO-2,6-t-Bu[sub 2]C[sub 6]H[sub 3] in refluxing toluene for 6 h provides U(O-2,6-R[sub 2]C[sub 6]H[sub 3])[sub 4] [R = t-Bu (11), i-Pr (12)]. While alcoholysis fails to provide the homoleptic Th(O-2,6-t-Bu[sub 2]C[sub 6]H[sub 3])[sub 4] (9), the authors can prepare this complex via a metathetical procedure. Reaction of ThI[sub 4](THF)[sub 4] with 4 equiv of KO-2,6-t-Bu[sub 2]C[sub 6]H[sub 3] in THF provides 9 in high yield.

• DOE Contract Number: W-7405-ENG-36
• OSTI ID: 7369111
• Journal Information: Journal of the American Chemical Society; (United States), Vol. 114:27; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
THORIUM COMPLEXES
CRYSTAL STRUCTURE
MOLECULAR STRUCTURE
URANIUM COMPLEXES
ABSORPTION SPECTROSCOPY
ADDUCTS
ALKOXIDES
CHEMICAL PREPARATION
CHEMICAL REACTION YIELD
INORGANIC POLYMERS
LATTICE PARAMETERS
MONOCLINIC LATTICES
NUCLEAR MAGNETIC RESONANCE
ORGANOMETALLIC COMPOUNDS
PHENOL
PYRIDINE
SILICON COMPOUNDS
STOICHIOMETRY
TETRAGONAL LATTICES
X-RAY DIFFRACTION
ACTINIDE COMPLEXES
AROMATICS
AZINES
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
DIFFRACTION
HETEROCYCLIC COMPOUNDS
HYDROXY COMPOUNDS
MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHENOLS
POLYMERS
PYRIDINES
RESONANCE
SCATTERING
SPECTROSCOPY
SYNTHESIS
YIELDS
400702* - Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials