New Benzylpotassium Reagents and Their Utility for the Synthesis of Homoleptic Uranium(IV) Benzyl Derivatives

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• 作者：Sara A. Johnson ; John J. Kiernicki ; Phillip E. Fanwick ; Suzanne C. Bart
• 刊名：Organometallics
• 出版年：2015
• 出版时间：June 22, 2015
• 年：2015
• 卷：34
• 期：12
• 页码：2889-2895
• 全文大小：337K
• ISSN：1520-6041

文摘

A new family of benzylpotassium reagents, KBn鈥?1-Bn鈥? (Bn鈥?= p-ⁱPrBn, p-^tBuBn, p-NMe₂Bn, p-SMeBn, m-OMeBn, o-OMeBn, 2-picolyl), was synthesized using a modified literature procedure and characterized by multinuclear NMR spectroscopy. Combining four equivalents of 1-Bn鈥?with UCl₄ at low temperature in THF afforded the homoleptic uranium(IV) derivatives 2-Bn鈥?(2-p-ⁱPr, 2-p-^tBu, 2-p-NMe₂, 2-p-SMe, 2-o-Picolyl, 2-m-OMe, 2-o-OMe). In addition to ¹H NMR spectroscopic characterization, structural studies of five of these organouranium compounds (2-p-ⁱPr, 2-p-^tBu, 2-o-Picolyl, 2-m-OMe, 2-o-OMe) were performed, showing that in many cases the benzyl groups are coordinated in an 畏⁴-fashion, lending stability to these otherwise low-coordinate molecules. In the cases of U(o-OMeBn)₄ (2-o-OMe) and U(2-picolyl)₄ (2-o-Picolyl), heteroatom coordination to the uranium center is observed.