A Singlet Biradicaloid Zinc Compound and Its Nonradical Counterpart

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• 作者：Amit Pratap Singh ; Prinson P. Samuel ; Herbert W. Roesky ; Martin C. Schwarzer ; Gernot Frenking ; Navdeep S. Sidhu ; Birger Dittrich
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：May 15, 2013
• 年：2013
• 卷：135
• 期：19
• 页码：7324-7329
• 全文大小：305K
• 年卷期：v.135,no.19(May 15, 2013)
• ISSN：1520-5126

文摘

Metal ions with radical centers in their coordination sphere are key participants in biological and catalytic processes. In the present study, we describe the synthesis of the cAAC:ZnCl₂ adduct (1) using a cyclic alkylaminocarbene (cAAC) as donor ligand. Compound 1 was treated with 2 equiv of KC₈ and LiB(sec-Bu)₃H to yield a deep blue-colored dicarbene zinc compound (cAAC)₂Zn (2) and the colorless hydrogenated zinc compound (cAACH)₂Zn (3), respectively. Compounds 2 and 3 were well characterized by spectroscopic methods and single-crystal X-ray structural analysis. Density functional theory calculations were performed for 2 which indicate that this molecule possesses a singlet biradicaloid character. Moreover, we show the application of 2 in CO₂ activation, which yields a zwitterionic cAAC路CO₂ adduct.