Details

Autor(en) / Beteiligte

• Li, Tongyu
• Wang, Dongwei
• Heng, Yi
• Hou, Guohua
• Zi, Guofu
• Ding, Wanjian
• Walter, Marc D.

Titel

A Comprehensive Study Concerning the Synthesis, Structure, and Reactivity of Terminal Uranium Oxido, Sulfido, and Selenido Metallocenes

Ist Teil von

• Journal of the American Chemical Society, 2023-07, Vol.145 (27), p.14839-14855

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2023

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Terminal uranium oxido, sulfido, and selenido metallocenes were synthesized, and their reactivity was comprehensively studied. Heating of an equimolar mixture of [η5-1,2,4-(Me3Si)3C5H2]2UMe2 (2) and [η5-1,2,4-(Me3Si)3C5H2]2U­(NH-p-tolyl)2 (3) in the presence of 4-dimethylaminopyridine (dmap) in refluxing toluene forms [η5-1,2,4-(Me3Si)3C5H2]2UN­(p-tolyl)­(dmap) (4), which is a useful precursor for the preparation of the terminal uranium oxido, sulfido, and selenido metallocenes [η5-1,2,4-(Me3Si)3C5H2]2UE­(dmap) (E = O (5), S (6), Se (7)) employing a cycloaddition–elimination methodology with Ph2CE (E = O, S) or (p-MeOPh)2CSe, respectively. Metallocenes 5–7 are inert toward alkynes, but they act as nucleophiles in the presence of alkylsilyl halides. The oxido and sulfido metallocenes 5 and 6 undergo [2 + 2] cycloadditions with isothiocyanate PhNCS or CS2, while the selenido derivative 7 does not. The experimental studies are complemented by density functional theory (DFT) computations.