Understanding Structure Does Not Always Explain Reactivity: A Phosphinoamide Anion Reacts as an Iminophosphide Anion

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• 作者：Zhaofu Fei ; Rosario Scopelliti ; and Paul J. Dyson
• 刊名：Inorganic Chemistry
• 出版年：2003
• 出版时间：March 24, 2003
• 年：2003
• 卷：42
• 期：6
• 页码：2125 - 2130
• 全文大小：144K
• 年卷期：v.42,no.6(March 24, 2003)
• ISSN：1520-510X

文摘

The aminophosphine C₆H₄(o-CN)NHPPh₂, 1, containing an electron-withdrawing nitrile group, was prepared fromthe lithiation of 2-aminobenzonitrile followed by addition of Ph₂PCl. Lithiation of 1 using ⁿBuLi affords the anion[Ph₂PN(Li)C₆H₄(o-CN)(thf)]₂, 2. Compound 2 reacts with Ph₂PCl or MeI to afford C₆H₄(o-CN)N=PPh₂-PPh₂, 3,and [C₆H₄(o-CN)N=PPh₂(CH₃)(LiI)(C₂H₅O)]₂, 4, respectively. In these products new P-P and P-C bonds havebeen formed rather than N-P and N-C bonds. The structures of 1-4 have been determined by single-crystalX-ray diffraction analysis, and the synthetic results are discussed in terms of the structural data and NMR spectroscopicstudies.