α-Cationic Arsines: Synthesis, Structure, Reactivity, and Applications
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- 作者：Jonathan W. Dube ; Yiying Zheng ; Walter Thiel ; Manuel Alcarazo
- 刊名：Journal of the American Chemical Society
- 出版年：2016
- 出版时间：June 1, 2016
- 年：2016
- 卷：138
- 期：21
- 页码：6869-6877
- 全文大小：640K
- 年卷期：0
- ISSN：1520-5126
文摘
A series of structurally differentiated cationic arsines containing imidazolium, cyclopropenium, formamidinium, and pyridinium substituents have been synthesized through short and scalable routes. Evaluation of the donor properties of these compounds by IR spectroscopy and DFT calculations reveals similar σ-electron-releasing abilities for all of them; however, their π-acceptor properties are strongly influenced by the nature of the positively charged group. We describe the coordination chemistry of the newly prepared α-cationic arsines toward different metal centers and their reactivity in the presence of strong oxidants to afford cationic As(V) species. Their unique electronic properties have been exploited in Pt(II) catalysis to develop a new catalyst with remarkable activity in the cycloisomerization of enynes to trisubstituted cyclopropanes. To the best of our knowledge, this is the first report on the use of α-cationic arsine ligands in catalysis.