Influence of the Lewis Base Ph3PO on the Reactivity of the Uranium Phosphinidene (η5-C5Me5)2U(=P-2,4,6-iPr3C6H2)(OPPh3)

This paper describes the synthesis, structure, and reactivity of (eta(5)-C5Me5)(2)U(=-P-2,4,6-(Pr3C6H2)-Pr-i)(OPPh3) (2). Compound 2 can be accessed by a salt metathesis reaction of the uranium methyl chloride metallocene (eta(5)-C5Me5)(2)U(Cl)Me (1) with 2,4,6-(Pr3C6H2PHK)-Pr-i in toluene in the presence of Ph3PO at ambient temperature. Furthermore, it reacts as a masked synthon for the divalent uranium fragment (eta(5)-C5Me5)(2)U by elimination of the phosphinidene fragment (2,4,6-(Pr3C6H2P)-Pr-i:) on exposure to small organic molecules such as Ph2S2, Ph2Se2, bipy, ketazines, carbodiimides, diazenes, and organic azides. Nevertheless, it also forms carbodithioates, imido, diiminatos, and metallaaziridines when it is treated with isothiocyanate, nitrites, and isonitriles, respectively. In contrast, after addition of Me,SiN 3 the uranium azido species (eta(5)-C5Me5)(2)U[N(SiMe3)P(2-NHCMe2-4,6-(Pr2C6H2)-Pr-i)N(SiMe3)]-(N-3) (13) is isolated in good yield.

Automated summary

This study describes the synthesis, structure, and reactivity of a new uranium-containing compound with high reactivity towards small organic molecules. Tests have shown that it undergoes various types of reactions when exposed to different organic molecules.