Synthesis and characterization of thorium tert-butoxide complexes: X-ray crystal structure sof Th(O-t-Bu)[sub 4](py)[sub 2] and NaTh[sub 2](O-t-Bu)[sub 9]
- Los Alamos National Lab., NM (United States)
Two synthetic procedures have been employed for the preparation of thorium tert-butoxide complexes. Reaction of ThI[sub 4](THF)[sub 4] with 4 equiv of KO-t-Bu in THF/pyridine solution provides Th(O-t-Bu)[sub 4](py)[sub 2] (1) in moderate yield. Alcoholysis of the thorium metallacycle [[l brace](Me[sub 3]Si)[sub 2]N[r brace][sub 2][ovr Th(CH[sub 2]SiMe[sub 2]N]SiMe[sub 3])] with >4 equiv of HO-t-Bu produces the dimeric alcoholate Th[sub 2](O-t-Bu)[sub 8](HO-t-Bu) (2) in 70% isolated yield. The coordinated alcohol in 2 is readily deprotonated by employing NaN(SiMe[sub 3])[sub 2] in hexane solution to provide hexane-soluble NaTh[sub 2](O-t-Bu)[sub 9] (3) in ca. 70% yield. Formation of the trimeric complex Th[sub 3]O(O-t-Bu)[sub 10] (4) occurs upon addition of stoichiometric amounts of H[sub 2]O to refluxing toluene solutions of 2. Compounds 1-4 have been characterized by elemental analysis, [sup 1]H NMR, infrared spectroscopy, and, for 1 and 3, single-crystal X-ray diffraction. In 1, the Th atom is coordinated to four alkoxide and two pyridine ligands in a cis pseudo-octahedral fashion with average Th-O and Th-N distances of 2.182(6) and 2.752(7) [Angstrom], respectively. In 3, the NaTh[sub 2](O-t-Bu)[sub 9] unit is closely related to the well-known M[sub 3]X[sub 11] cluster and is best described as NaTh[sub 2]([mu][sub 3]-O-t-Bu)[sub 2]([mu][sub 2]-O-t-Bu)[sub 4]. Averaged Na-[mu][sub 3]-O and Na-[mu][sub 2]-O distances are 2.399(17) and 2.607(10) [Angstrom], respectively. Th-O distances are 2.155(8), 2.280(10), 2.464(7), and 2.491(7) [Angstrom] for terminal, doubly bridging to sodium, doubly bridging to thorium, and triply bridging alkoxides, respectively. 40 refs., 2 figs., 7 tabs.
- DOE Contract Number:
- W-7405-ENG-36
- OSTI ID:
- 6257429
- Journal Information:
- Inorganic Chemistry; (United States), Vol. 32:9; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ALKOXIDES
MOLECULAR STRUCTURE
THORIUM COMPLEXES
ABSORPTION SPECTROSCOPY
BOND LENGTHS
CHEMICAL REACTION YIELD
CRYSTAL STRUCTURE
LIGANDS
NUCLEAR MAGNETIC RESONANCE
PYRIDINE
SODIUM COMPOUNDS
X-RAY DIFFRACTION
ACTINIDE COMPLEXES
ALKALI METAL COMPOUNDS
AZINES
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
DIMENSIONS
HETEROCYCLIC COMPOUNDS
LENGTH
MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
RESONANCE
SCATTERING
SPECTROSCOPY
YIELDS
400702* - Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials