Small Molecule Activation Mediated by a Thorium Terminal Imido Metallocene

Abstract

(Chemical Equation Presented). The base-free thorium terminal imido [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 Thi=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, Ph 2 NH, 9-borabicyclo[3.3.1]nonane (9-BBN), PhSiH 2 Cl, elemental selenium, PhSeSePh, and methyl methacrylate (MMA) formed the amido pyridyl complexes [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 Th(NH-p-tolyl)(η 2 -C,N-C 5 H 4 N) (2), [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 Th(NH-p-tolyl)(κ 2 -C,O-C 5 H 4 NO) (3), and [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 Th(NH-p-tolyl)(κ 2 -C,O-2-MeC 5 H 3 NO) (4), diamide complexes [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 Th(NH-p-tolyl) 2 (5) and [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 Th(NH-p-tolyl)(NPh 2) (6), amido hydrido complex [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 Th(H)[N(p-tolyl)B(C 8 H 14)] (7), amido chloride complex [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 Th(Cl)[N(p-tolyl)SiH 2 Ph] (8), amido selenido complexes [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 Th[N(p-tolyl)Se-Se] (9) and {[η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ]Th(SePh)} 2 [μ-N(p-tolyl)] 2 (10), and amido enolyl complex [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 Th[N(p-tolyl)CH 2 C(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.