Reactivity of a Lewis base-supported uranium terminal imido metallocene towards small molecules.

The Lewis base-supported uranium terminal imido metallocene [η5-1,2,4-(Me3Si)3C5H2]2UN(p-tolyl)(dmap) (1) readily reacts with various small molecules such as internal alkynes, isothiocyanates, thioketones, amidates, organic nitriles and imines, chlorosilanes, copper iodide, diphenyl disulfide, organic azides and diazoalkane derivatives. For example, treatment of 1 with PhCCCCPh and PhNCS forms metallaheterocycles originating from a [2 + 2] cycloaddition to yield [η5-1-(p-tolyl)NC(Ph)CHCC(Ph)CH2Si(Me)2-2,4-(Me3Si)2C5H2][η5-1,2,4-(Me3Si)3C5H2]U (2) and [η5-1,2,4-(Me3Si)3C5H2]2U[N(p-tolyl)C(NPh)S](dmap) (3), respectively. The reaction of 1 with the thioketone Ph2CS forms the known uranium sulfido complex [η5-1,2,4-(Me3Si)3C5H2]2US(dmap) (4), which reacts with a second molecule of Ph2CS to give the disulfido compound [η5-1,2,4-(Me3Si)3C5H2]2U(S2CPh2) (5). The imido moiety also promotes deprotonation reactions as illustrated in the reactions with the amide PhCONH(p-tolyl), the nitrile PhCH2CN and the imine (p-tolyl)2CNH to form the bis-amidate [η5-1,2,4-(Me3Si)3C5H2]2U[OC(Ph)N(p-tolyl)]2 (7), and the iminato complexes [η5-1,2,4-(Me3Si)3C5H2]2U[N(p-tolyl)C(CH2Ph)NH](NCCHPh) (8) and [η5-1,2,4-(Me3Si)3C5H2]2U[NH(p-tolyl)][NC(p-tolyl)2] (9), respectively. Addition of PhSiH2Cl to 1 yields [η5-1,2,4-(Me3Si)3C5H2]2U(Cl)[N(p-tolyl)SiH2Ph] (10). In contrast, the uranium(V) imido complexes [η5-1,2,4-(Me3Si)3C5H2]2UN(p-tolyl)(I) (11) and [η5-1,2,4-(Me3Si)3C5H2]2UN(p-tolyl)(SPh) (12), may be isolated upon addition of CuI or Ph2S2 to 1, respectively. Uranium(VI) bis-imido metallocenes [η5-1,2,4-(Me3Si)3C5H2]2UN(p-tolyl)(NR) (R = p-tolyl (13), mesityl (14)) and [η5-1,2,4-(Me3Si)3C5H2]2UN(p-tolyl)[NN(9-C13H8)] (15) are accessible from 1 on exposure to RN3 (R = p-tolyl, mesityl) and 9-diazofluorene, respectively. Complexes 2, 3, 5, and 7-15 were characterized by various spectroscopic techniques and, in addition, compounds 2, 3, 5, and 7-13 were structurally authenticated by single-crystal X-ray diffraction analyses.