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(p-tolyl)]2 (10), and amido enolyl
complex [η5-1,2,4-(Me3C)3C5H2]2Th­[N­(p-tolyl)­CH2C­(Me)C­(OMe)­O] (11). The new complexes 2–3 and 6–11 were characterized by various spectroscopic techniques including
single crystal X-ray diffraction. Furthermore, density functional
theory (DFT) studies complement the experimental investigations.