Small Molecule Activation Mediated by a Thorium Terminal Imido Metallocene

The base-free thorium terminal imido [η5-1,2,4-(Me3C)3C5H2]2Th═N(p-tolyl) (1) activates a variety of small molecules such as pyridine derivatives, amines, boranes, chlorosilane, elemental selenium, and α,β-unsaturated esters. Reaction of 1 with pyridine, pyridine N-oxide, 2-methylpyridine N-oxide, p-toluidine, Ph2NH, 9-borabicyclo[3.3.1]nonane (9-BBN), PhSiH2Cl, elemental selenium, PhSeSePh, and methyl methacrylate (MMA) formed the amido pyridyl complexes [η5-1,2,4-(Me3C)3C5H2]2Th(NH-p-tolyl)(η2-C,N-C5H4N) (2), [η5-1,2,4-(Me3C)3C5H2]2Th(NH-p-tolyl)(κ2-C,O-C5H4NO) (3), and [η5-1,2,4-(Me3C)3C5H2]2Th(NH-p-tolyl)(κ2-C,O-2-MeC5H3NO) (4), diamide complexes [η5-1,2,4-(Me3C)3C5H2]2Th(NH-p-tolyl)2 (5) and [η5-1,2,4-(Me3C)3C5H2]2Th(NH-p-tolyl)(NPh2) (6), amido hydrido complex [η5-1,2,4-(Me3C)3C5H2]2Th(H)[N(p-tolyl)B(C8H14)] (7), amido chloride complex [η5-1,2,4-(Me3C)3C5H2]2Th(Cl)[N(p-tolyl)SiH2Ph] (8), amido selenido complexes [η5-1,2,4-(Me3C)3C5H2]2Th[N(p-tolyl)Se–Se] (9) and {[η5-1,2,4-(Me3C)3C5H2]Th(SePh)}2[μ-N...