Reactivity studies involving a Lewis base supported terminal uranium phosphinidene metallocene [η5-1,3-(Me3C)2C5H3]2U(=P-2,4,6-iPr3C6H2) (OPMe3)

The Lewis base supported terminal uranium phosphinidene metallocene [eta(5)-1,3-(Me3C)(2)C5H3](2)U(=P-2,4,6-(Pr3C6H2)-Pr-i)(OPMe3) (2) could be isolated from a salt metathesis reaction in toluene at ambient temperature between [eta(5)-1,3-(Me3C)(2)C5H3](2)U(Cl)Me (1) and 2,4,6-(Pr3C6H2PHK)-Pr-i in the presence of Me3PO, and its structure and reactivity were probed in detail. No reaction of 2 with internal alkynes was observed, but it reacts in the presence of various heterounsaturated molecules such as CS2, isothiocyanates, aldehydes, imines, diazenes, carbodiimides, nitriles, isonitriles, diazoalkane, and organic azides, forming carbodithioates, sulfidos, oxidos, metallaheterocycles, and imido complexes, in good yields. Moreover, on reaction with the diazoalkane derivative Me3SiCHN2 the pseudophosphinimido uranium(III) complex [eta(5)-1,3-(Me3C)(2)C5H3](2)U(N=P-2,4,6-(Pr3C6H2)-Pr-i)(OPMe3) (20) can be isolated in good yield.

Automated summary

A novel terminal uranium phosphinidene metallocene complex was isolated and its reactivity towards various heterounsaturated molecules was investigated, leading to the formation of carbodithioates, sulfidos, oxidos, metallaheterocycles, and imido complexes in good yields. Additionally, a pseudophosphinimido uranium(III) complex was obtained in good yield by reacting with a diazoalkane derivative. This study provides new insights into the synthesis and applications of organouranium complexes.