Habicht Marija H, Wossidlo Friedrich, Bens Tobias, Pidko Evgeny A, Müller Christian
Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34/36, 14195, Berlin, Germany.
ITMO University, Lomonosova 9, St. Petersburg, 191002, Russia.
Chemistry. 2018 Jan 19;24(4):944-952. doi: 10.1002/chem.201704539. Epub 2017 Dec 11.
The [4+2] cycloaddition reaction between 2-pyrone and Me Si-C≡P gives the corresponding 2-(trimethylsilyl)-λ -phosphinine in good yields as a rather air and moisture stable, colorless oil. Insight into the regioselectivity of the pericyclic reaction was obtained with the help of deuterium-labeling experiments. The silyl-phosphinine acts as a ligand for the preparation of a Cu(I) and the first crystallographically characterized phosphinine-Ag(I) complex. The title compound was further used as a starting material for an alternative preparation of the parent phosphinine C H P by means of protodesilylation with HCl. C H P reacts with CuBr⋅S(CH ) to give an infinite Cu(I)Br coordination polymer. DFT calculations shed light on the influence of the -Si(CH ) group on the electronic properties of the aromatic phosphorus heterocycle.
2-吡喃酮与MeSi-C≡P之间的[4+2]环加成反应能以良好的产率得到相应的2-(三甲基硅基)-λ⁵-磷杂苯，它是一种相当稳定、对空气和湿气稳定的无色油状物。借助氘标记实验深入了解了该周环反应的区域选择性。硅基磷杂苯用作制备Cu(I)配合物以及首个经晶体学表征的磷杂苯-Ag(I)配合物的配体。标题化合物还被用作通过用HCl进行去甲硅烷基化反应来另一种制备母体磷杂苯C₅H₅P的起始原料。C₅H₅P与CuBr⋅S(CH₃)₂反应生成一种无限的Cu(I)Br配位聚合物。密度泛函理论计算揭示了-Si(CH₃)₃基团对芳香族磷杂环电子性质的影响。
