Phosphido- and Amidozirconocene Cation-Based Frustrated Lewis Pair Chemistry

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• 作者：Adrien T. Normand ; Constantin G. Daniliuc ; Birgit Wibbeling ; Gerald Kehr ; Pierre Le Gendre ; Gerhard Erker
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：August 26, 2015
• 年：2015
• 卷：137
• 期：33
• 页码：10796-10808
• 全文大小：772K
• ISSN：1520-5126

文摘

Methyl abstraction from neutral [Cp₂ZrMe(ERR鈥?] complexes 1 (E = N, P; R, R鈥?= alkyl, aryl) with either B(C₆F₅)₃ or [Ph₃C][B(C₆F₅)₄] results in the formation of [Cp₂Zr(ERR鈥?][X] complexes 2 (X^{鈥?/sup> = MeB(C₆F₅)₃鈥?/sup>, B(C₆F₅)₄鈥?/sup>). The X-ray structure of amido complexes [Cp₂Zr(NPh₂)][MeB(C₆F₅)₃] (2d) and [Cp₂Zr(NtBuAr)][B(C₆F₅)₄] (2e鈥? Ar = 3,5-C₆H₃(CH₃)₂) is reported, showing a sterically dependent Zr/N鈭捪€ interaction. Complexes 2 catalyze the hydrogenation of electron-rich olefins and alkynes under mild conditions (room temperature, 1.5 bar H₂). Complex 2e binds CO₂, giving [Cp₂Zr(CO₂)(NtBuAr)]₂[MeB(C₆F₅)₃]₂ (3e). Amido complex 2d reacts with benzaldehyde yielding [Cp₂Zr(OCH₂Ph)((OC)PhNPh₂)][MeB(C₆F₅)₃] (7d). Phosphido complex [Cp₂Zr(PCy₂)][MeB(C₆F₅)₃] (2a) reacts with diphenylacetylene to yield frustrated Lewis pair [Cp₂Zr(PhCCPh)(PCy₂)][MeB(C₆F₅)₃] (8a) which further reacts with a range of carbonyl substrates.}