Synthesis, characterization, and X-ray structure of the uranium thiolate complex U(S-2,6-Me[sub 2]C[sub 6]H[sub 3])[N(SiMe[sub 3])[sub 2]][sub 3]

Journal Article · Wed Mar 03 00:00:00 EST 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00057a044· OSTI ID:6724244

Clark, D L; 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)

Due to the paucity of actinide thiolate complexes reported to date, it was of interest to examine the corresponding reactions between the actinide metallacycle [[l brace](Me[sub 3]Si)[sub 2]N[r brace][sub 2][ovr An(CH[sub 2]SiMe[sub 2]N]SiMe[sub 3])] and substituted arenethiol reagents in an attempt to prepare homoleptic thiolate complexes An(SAr)[sub 4]. In contrast to the relatively clean products obtained by reaction with disubstituted phenols, treatment of the uranium metallacycle [[l brace](Me[sub 3]Si)[sub 2]N[r brace][sub 2][ovr U(CH[sub 2]SiMe[sub 2]N]SiMe[sub 3])] with 4 equiv of 2,6-disubstituted arenethiol yielded highly insoluble, intractable products. The nature of these products is still under investigation although the authors believe that they could be uranium sulfides. They have determined however, that treatment of a toluene solution of the uranium metallacycle [[l brace](Me[sub 3]Si)[sub 2]N[r brace][sub 2][ovr U(CH[sub 2]SiMe[sub 2]N]SiMe[sub 3])] with 1 equiv of 2,6-dimethylthiophenol at room temperature, followed by crystallization from 1:1 toluene/hexane, gives the brown crystalline monothiolate U(S-2,6-Me[sub 2]C[sub 6]H[sub 3])[N(SiMe[sub 3])[sub 2]][sub 3] (1) in good yield. U(S-2,6-Me[sub 2]C[sub 6]H[sub 3])[N(SiMe[sub 3])[sub 2]][sub 3] and additional equivalents of arenethiol gives intractable products, even at low temperature. Four-coordinate early actinide complexes are relatively rare, and thus they describe here the X-ray structure of the monothiolate U(S-2,6-Me[sub 2]C[sub 6]H[sub 3])[N(SiMe[sub 3])[sub 2]][sub 3] and some of its physical and spectroscopic properties. 22 refs., 1 fig., 3 tabs.

• DOE Contract Number: W-7405-ENG-36
• OSTI ID: 6724244
• Journal Information: Inorganic Chemistry; (United States), Vol. 32:5; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
SULFUR COMPOUNDS
CHEMICAL PREPARATION
MOLECULAR STRUCTURE
URANIUM COMPLEXES
CRYSTAL STRUCTURE
NUCLEAR MAGNETIC RESONANCE
X-RAY DIFFRACTION
ACTINIDE COMPLEXES
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
MAGNETIC RESONANCE
RESONANCE
SCATTERING
SYNTHESIS
400702* - Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials