Lewis Base Activation by Uranium(III) Complexes
The combination of a bulky hypersilyl potassium [(Me3Si)3SiK] reagent with Tp*2UI (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) in the presence of ethereal Lewis donors resulted in the formation of base-activated products Tp*2U[O(CH2)4Si(SiMe3)3] (1-THF) and Tp*2U[O(CH2)2OMe] (2-DME). The re...
Gespeichert in:
Veröffentlicht in: | Organometallics 2023-04, Vol.42 (8), p.641-650 |
---|---|
Hauptverfasser: | , , , , |
Format: | Artikel |
Sprache: | eng |
Online-Zugang: | Volltext |
Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
Zusammenfassung: | The combination of a bulky hypersilyl potassium [(Me3Si)3SiK] reagent with Tp*2UI (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) in the presence of ethereal Lewis donors resulted in the formation of base-activated products Tp*2U[O(CH2)4Si(SiMe3)3] (1-THF) and Tp*2U[O(CH2)2OMe] (2-DME). The reactivity with another Lewis base, pyridine, was explored by treating Tp*2UI and hypersilyl potassium or benzyl potassium in the presence of pyridine, which resulted in formation of Tp*2U[NC5H5-4-Si(SiMe3)3] (3-py-Si) and Tp*2U(NC5H5-4-Bn) (4-py-Bn, Bn = benzyl), respectively. Multinuclear paramagnetic NMR spectroscopy (1H, 11B{1H}, 29Si{1H}) supported the formation of the Lewis base activated uranium compounds as corroborated by electronic absorption spectroscopy and X-ray crystallography. To recognize the mechanistic possibilities, radical trap experiments were performed and [K(18-crown-6)][4-benzylpyridinide] (4-K), Tp*U(IV)[(NC(Me)C(H)C(Me)N)-B(H)(3,5-dimethylpyrazole)2] (6-Tp*UTp′), and [Tp*2U(NC5H5)]2 (5-py-py) were observed. |
---|---|
ISSN: | 0276-7333 1520-6041 |
DOI: | 10.1021/acs.organomet.2c00633 |