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

Abstract

The Lewis base supported terminal uranium phosphinidene metallocene [η⁵-1,3-(Me₃C)₂C₅H₃]₂U(P-2,4,6-ⁱPr₃C₆H₂)(OPMe₃) (2) could be isolated from a salt metathesis reaction in toluene at ambient temperature between [η⁵-1,3-(Me₃C)₂C₅H₃]₂U(Cl)Me (1) and 2,4,6-ⁱPr₃C₆H₂PHK 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 [η⁵-1,3-(Me₃C)₂C₅H₃]₂U(NP-2,4,6-ⁱPr₃C₆H₂)(OPMe₃) (20) can be isolated in good yield.