Small Molecule Activation Mediated by a Thorium Terminal Imido Metallocene

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• 作者：Enwei Zhou ; Wenshan Ren ; Guohua Hou ; Guofu Zi ; De-Cai Fang ; Marc D. Walter
• 刊名：Organometallics
• 出版年：2015
• 出版时间：July 27, 2015
• 年：2015
• 卷：34
• 期：14
• 页码：3637-3647
• 全文大小：789K
• ISSN：1520-6041

文摘

The base-free thorium terminal imido [畏⁵-1,2,4-(Me₃C)₃C₅H₂]₂Th鈺怤(p-tolyl) (1) activates a variety of small molecules such as pyridine derivatives, amines, boranes, chlorosilane, elemental selenium, and 伪,尾-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 [畏⁵-1,2,4-(Me₃C)₃C₅H₂]₂Th(NH-p-tolyl)(畏²-C,N-C₅H₄N) (2), [畏⁵-1,2,4-(Me₃C)₃C₅H₂]₂Th(NH-p-tolyl)(魏²-C,O-C₅H₄NO) (3), and [畏⁵-1,2,4-(Me₃C)₃C₅H₂]₂Th(NH-p-tolyl)(魏²-C,O-2-MeC₅H₃NO) (4), diamide complexes [畏⁵-1,2,4-(Me₃C)₃C₅H₂]₂Th(NH-p-tolyl)₂ (5) and [畏⁵-1,2,4-(Me₃C)₃C₅H₂]₂Th(NH-p-tolyl)(NPh₂) (6), amido hydrido complex [畏⁵-1,2,4-(Me₃C)₃C₅H₂]₂Th(H)[N(p-tolyl)B(C₈H₁₄)] (7), amido chloride complex [畏⁵-1,2,4-(Me₃C)₃C₅H₂]₂Th(Cl)[N(p-tolyl)SiH₂Ph] (8), amido selenido complexes [畏⁵-1,2,4-(Me₃C)₃C₅H₂]₂Th[N(p-tolyl)Se鈥揝e] (9) and {[畏⁵-1,2,4-(Me₃C)₃C₅H₂]Th(SePh)}₂[渭-N(p-tolyl)]₂ (10), and amido enolyl complex [畏⁵-1,2,4-(Me₃C)₃C₅H₂]₂Th[N(p-tolyl)CH₂C(Me)鈺怌(OMe)O] (11). The new complexes 2鈥?b>3 and 6鈥?b>11 were characterized by various spectroscopic techniques including single crystal X-ray diffraction. Furthermore, density functional theory (DFT) studies complement the experimental investigations.