A Lewis Base Supported Terminal Uranium Phosphinidene Metallocene

Abstract

A Lewis base supported terminal uranium phosphinidene, [η⁵-1,3-(Me₃C)₂C₅H₃]₂U(═P-2,4,6-^<i>t</i>Bu₃C₆H₂)(OPMe₃) (<b>5</b>), is isolated from the reaction of the uranium methyl chloride [η⁵-1,3-(Me₃C)₂C₅H₃]₂U(Cl)Me (<b>4</b>) with 2,4,6-(Me₃C)₃C₆H₂PHK in toluene in the presence of Me₃PO. Moreover, the reactivity of uranium phospinidene <b>5</b> toward a series of small molecules was comprehensively explored. While no reactivity of <b>5</b> with internal alkynes is observed attributed to steric hindrance, it readily reacts in good yields with various small molecules including isothiocyanates, aldehydes, imines, diazenes, carbodiimides, nitriles, isonitriles, and organic azides, yielding uranium sulfidos, oxidos, metallaheterocycles, and imido complexes.