砷杂炔烃
合成与分离
砷杂炔烃可由脱卤化氢反应或碱引发的消除反应制得,如HCAs由下式反应得到:
- H
2ClCAsH
2 + 2 Na
2CO
3 → HCAs + 2 NaHCO
3 + 2 NaCl
根据双键规则,砷杂炔烃有低聚倾向,试图制备AsCCMe3时,只会得到具有立方烷结构的四聚体。[2]具有很大位阻取代基的C6H2-2,4,6-(t-Bu)3可以以单体的形式结晶出来,其As-C键的键长为1.657(7) Å。[3]
参见
参考文献
- ^ Guillemin, Jean-Claude; Chrostowska, Anna; Dargelos, Alain; Nguyen, Thi Xuan Mai; Graciaa, Alain; Guenot, Pierre. Methylidynearsine (HC≡As): Synthesis and Direct Characterization by UV-Photoelectron Spectroscopy and Mass Spectrometry. Chemical Communications. 2008, (35): 4204–4206. PMID 18802530. doi:10.1039/B806771F.
- ^ Hitchcock, Peter B.; Johnson, Julian A.; Nixon, John F. Synthesis and Structure of the Arsaalkyne Tetramer (AsCtBu)4 and its Fe(CO)4 Derivative. Angewandte Chemie International Edition in English. 1993, 32: 103–104. doi:10.1002/anie.199301031.
- ^ Hitchcock, Peter B.; Jones, Cameron; Nixon, John F. Synthesis, Crystal and Molecular Structure of the First Metal Complex [Pt(PPh3)2{η2-As≡C(C6H2But3)}] Derived from an Arsaalkyne. J. Chem. Soc., Chem. Commun. 1994, (18): 2061–2062. doi:10.1039/C39940002061.