Facile solution routes to hydrocarbon-soluble Lewis base adducts of thorium tetrahalides. Synthesis, characterization, and X-ray structure of ThBr[sub 4](THF)[sub 4]

Journal Article · Wed Apr 29 04:00:00 EDT 1992 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00035a021· OSTI ID:6915925

Clark, D L; Frankcom, T M; Watkin, J G ^[1]; Miller, M M ^[2]

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1. Los Alamos National Lab., NM (United States)
2. Colorado State Univ., Fort Collins (United States)

The direct combination of thorium metal turnings with 2 equiv of elemental bromine or iodine in THF solution at 0C provides white crystalline ThX[sub 4](THF)[sub 4] (X = Br, 1; X = 1,2; THF = tetrahydrofuran), in 70-80% isolated yield. These new compounds are soluble in hydrocarbon solvents and react readily with oxygen- and nitrogen-donor ligands in toluene solution to give ThBr[sub 4]py[sub 4] (3), ThI[sub 4]py[sub 4] (4), ThBr[sub 4](NCMe)[sub 4], (5), and ThBr[sub 4](DME)[sub 2] (6) in high yield (py = pyridine, DME = 1,2-dimethoxyethane). Compounds 1-6 have been characterized by elemental and thermogravimetric analysis, [sup 1]H NMR, infrared, and diffuse-reflectance spectroscopy, and, for 1, a single-crystal X-ray structure determination. The X-ray diffraction study of 1 revealed a slightly distorted dodecahedral coordination geometry about the central thorium atom with two interpenetrating tetrahedra of bromide and THF ligands. Oxygen atoms of the THF ligands occupy A vertices (Th-O = 2.549 (17) [angstrom], average) and bromide ions occupy B vertices (Th-Br = 2.859 (3) [angstrom], average) of an irregular dodecahedron. 1 is an excellent synthetic precursor to thorium coordination and organometallic complexes and can be prepared on a 100-150-g scale in a single day. 1 crystallizes in the rhombohedral space group.

• DOE Contract Number: W-7405-ENG-36
• OSTI ID: 6915925
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 31:9; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACTINIDE COMPLEXES
ACTINIDE COMPOUNDS
BOND ANGLE
BOND LENGTHS
BROMIDES
BROMINE
BROMINE COMPOUNDS
CHEMICAL ANALYSIS
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
CRYSTALS
DIFFRACTION
DIMENSIONS
ELEMENTS
GRAVIMETRIC ANALYSIS
HALIDES
HALOGEN COMPOUNDS
HALOGENS
INFRARED SPECTRA
IODIDES
IODINE
IODINE COMPOUNDS
KINETICS
LENGTH
LIGANDS
MONOCRYSTALS
NMR SPECTRA
NONMETALS
ORGANIC SOLVENTS
QUANTITATIVE CHEMICAL ANALYSIS
REACTION KINETICS
SCATTERING
SOLVENTS
SPECTRA
SYNTHESIS
THERMAL ANALYSIS
THERMAL GRAVIMETRIC ANALYSIS
THORIUM BROMIDES
THORIUM COMPLEXES
THORIUM COMPOUNDS
THORIUM IODIDES
X-RAY DIFFRACTION