Thermal Chemistry of Cp*W(NO)(H)(畏3-allyl) Complexes

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• 作者：Rhett A. Baillie ; Russell J. Wakeham ; Guillaume P. Lef猫vre ; Aur茅lien B茅thegnies ; Brian O. Patrick ; Peter Legzdins ; Devon C. Rosenfeld
• 刊名：Organometallics
• 出版年：2015
• 出版时间：July 13, 2015
• 年：2015
• 卷：34
• 期：13
• 页码：3428-3441
• 全文大小：798K
• ISSN：1520-6041

文摘

The thermal properties of Cp*W(NO)(H)(畏³-CH₂CHCMe₂) (1), Cp*W(NO)(H)(畏³-CH₂CHCHPh) (2), and Cp*W(NO)(H)(畏³-CH₂CHCHMe) (3) (Cp* = 畏⁵-C₅Me₅) have been investigated. Thermolyses of 1鈥?b>3 in n-pentane lead to the loss of the original allyl ligand and the formation of the same mixture of isomeric products, namely, Cp*W(NO)(H)(畏³-CH₂CHCHEt) (4a) and Cp*W(NO)(H)(畏³-MeCHCHCHMe) (4b) and their coordination isomers. Similarly, 1 reacts with cyclohexane and n-heptane to form Cp*W(NO)(H)(畏³-C₆H₉) and isomers of Cp*W(NO)(H)(畏³-C₇H₁₃), respectively. It is likely that complexes 1鈥?b>3 first effect the selective, single-terminal C鈥揌 activation of the linear alkanes, but the first-formed products are thermally unstable and undergo two additional successive C鈥揌 activations to form the final allyl complexes. Consistent with this view is the fact that a bis(alkyl) intermediate complex can be trapped with N-methylmorpholine. Thus, the thermolysis of 1 in N-methylmorpholine affords a single organometallic complex, Cp*W(NO)(畏²-CH₂NC₄H₈O)(畏¹-CH₂CH₂CHMe₂) (7). Complexes 2 and 3 react with N-methylmorpholine in an identical manner. Finally, 1 effects the multiple C鈥揌 activations of 1-chloropropane and 1-chlorobutane and forms the corresponding Cp*W(NO)(Cl)(畏³-allyl) complexes. All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.