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), Journal Name: Inorganic Chemistry; (United States) Vol. 32:9; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ABSORPTION SPECTROSCOPY
ACTINIDE COMPLEXES
ALKALI METAL COMPOUNDS
ALKOXIDES
AZINES
BOND LENGTHS
CHEMICAL REACTION YIELD
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DIFFRACTION
DIMENSIONS
HETEROCYCLIC COMPOUNDS
LENGTH
LIGANDS
MAGNETIC RESONANCE
MOLECULAR STRUCTURE
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINE
PYRIDINES
RESONANCE
SCATTERING
SODIUM COMPOUNDS
SPECTROSCOPY
THORIUM COMPLEXES
X-RAY DIFFRACTION
YIELDS