A homoleptic uranium thiolate: Synthesis, structure, and fluxional behavior of (Li(dme)) sub 4 (U(SCH sub 2 CH sub 2 S) sub 4 ) and reaction with CS sub 2

Journal Article · Wed Nov 28 00:00:00 EST 1990 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00349a021· OSTI ID:5872884

Tatsumi, Kazuyuki; Matsubara, Ichiro; Inoue, Yoshihisa; Nakamura, Akira ^[1]; Cramer, R E; Tagoshi, G J; Golen, J A; Gilje, J W ^[2]

---

1. Osaka Univ. (Japan)
2. Univ. of Hawaii, Honolulu (USA)

We have synthesized and fully characterized a tetrakis(ethane-1,2-dithiolato)uranate(IV), (Li(dme)){sub 4}(U(edt){sub 4}) (1), the first homoleptic dithiolate complex of an f element. The complex crystallizes with an additional DME solvent molecule, and its structure was determined by an x-ray study. The coordination geometry about the uranium center is dodecahedral, and four lithium cations surround the (U(edt){sub 4}){sup 4{minus}} anion. Each lithium bridges two sulfur atoms and is further coordinated by a dme molecule. We have analyzed the nature of the U-S bonds, using the extended Hueckel method, to find that U 6d, 7s, and 7p orbitals are responsible for interactions with sulfur orbitals, thus, no significant U 5f participation in bonding is discernible, and that U-S {pi} interactions are weak. The low temperature {sup 1}H NMR spectra in the THF-d{sub 8} exhibit four resonances associated with the edt protons. The relative size of their paramagnetic isotropic shifts can be interpreted on the basis of the pseudocontact (dipolar) term, the analysis of which suggests the solid-state dodecahedral structure to be retained in solution. The thermodynamic properties and crystal structure of the complex was determined, and they are reported herein. 53 refs., 5 figs., 8 tabs.

• OSTI ID: 5872884
• Journal Information: Inorganic Chemistry; (USA), Vol. 29:24; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
ALKANES
SYNTHESIS
LITHIUM COMPLEXES
THIOLS
URANATES
CARBON SULFIDES
CHEMICAL REACTIONS
CRYSTAL STRUCTURE
EXPERIMENTAL DATA
MOLECULAR STRUCTURE
ACTINIDE COMPOUNDS
CARBON COMPOUNDS
CHALCOGENIDES
COMPLEXES
DATA
HYDROCARBONS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
SULFIDES
SULFUR COMPOUNDS
URANIUM COMPOUNDS
400702* - Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials