Experimental and Computational Studies on an Actinide Metallacyclocumulene Complex

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• 作者：Bo Fang ; Lei Zhang ; Guohua Hou ; Guofu Zi ; De-Cai Fang ; Marc D. Walter
• 刊名：Organometallics
• 出版年：2015
• 出版时间：December 14, 2015
• 年：2015
• 卷：34
• 期：23
• 页码：5669-5681
• 全文大小：977K
• ISSN：1520-6041

文摘

Reduction of (畏⁵-C₅Me₅)₂ThCl₂ (1) with potassium graphite (KC₈) in the presence of 1,4-diphenylbutadiyne (PhC鈮C鈮Ph) yields the first actinide metallacyclocumulene, the thorium metallacyclopentatriene (畏⁵-C₅Me₅)₂Th(畏⁴-C₄Ph₂) (2). The structure and reactivity of 2 were investigated in detail; structural parameters and density functional theory (DFT) studies confirm the presence of a metallacyclopentatriene unit in 2. Furthermore, DFT computations also indicate a notable contribution of the 5f orbitals to the bonding of the metallacyclopentatriene Th鈥?畏⁴-C鈺怌鈺怌鈺怌) moiety. While complex 2 shows no reactivity toward alkynes, it reacts with a variety of heterounsaturated molecules such as isothiocyanates, carbodiimides, aldehydes, ketones, nitriles, pyridines, and diazoalkane derivatives. DFT studies complement the experimental observations and provide additional insights. Furthermore, in comparison to group 4 metals, the thorium metallacyclopentatriene 2 exhibits distinctively different reactivity patterns.