Preparation of (η5-C5Me5)2Th(bipy) and Its Reactivity toward Small Molecules

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• 作者：Pikun Yang ; Enwei Zhou ; Bo Fang ; Guohua Hou ; Guofu Zi ; Marc D. Walter
• 刊名：Organometallics
• 出版年：2016
• 出版时间：June 27, 2016
• 年：2016
• 卷：35
• 期：12
• 页码：2129-2139
• 全文大小：666K
• 年卷期：0
• ISSN：1520-6041

文摘

Reduction of (η⁵-C₅Me₅)₂ThCl₂ (1) with potassium graphite (KC₈) in the presence of 2,2′-bipyridine forms the thorium bipy metallocene (η⁵-C₅Me₅)₂Th(bipy) (2) in good yield. Complex 2 was fully characterized and reacts with various small molecules. For example, 2 serves as a source for the (η⁵-C₅Me₅)₂Th(II) fragment when exposed to conjugated alkynes, elemental sulfur and their organic derivatives, diazabutadiene, carbodiimide, CS₂, isothiocyanate, and organic azides. Furthermore, treatment of 2 with ketone Ph₂CO, thio-ketone Ph₂CS, imine PhCH═NPh, and nitrile PhCN results in C–C bond coupling products (η⁵-C₅Me₅)₂Th[(bipy)(Ph₂CO)] (10), (η⁵-C₅Me₅)₂Th[(bipy)(Ph₂CS)] (11), (η⁵-C₅Me₅)₂Th[(bipy)(PhCHNPh)] (12), and (η⁵-C₅Me₅)₂Th[(bipy)(PhCN)] (13), respectively, in quantitative conversion.