Kozma Ágnes, Rust Jörg, Alcarazo Manuel
Max-Planck-Institut für Kohlenforschung, Kaiser Wilhelm Platz 1, 45470 Mülheim an der Ruhr (Germany).
Chemistry. 2015 Jul 20;21(30):10829-34. doi: 10.1002/chem.201500688. Epub 2015 Jun 19.
The treatment of bis[(dialkylamino)cyclopropenimines] with dihalophosphines in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) to form diimine-stabilized P(III) -centered dications is reported. The structures of the new compounds were determined by using X-ray diffraction analysis and their donor abilities as ligands evaluated through electrochemical methods. Despite the two positive charges that they bear, these compounds depict intermediate behavior between that of phosphines and phosphites. The coordination of the L2 PR moiety to Au(I) and Ag(I) is also reported. Even more surprisingly, these phosphorus centers can be oxidized to the corresponding P(V) dications in the presence of strong oxidants such as peroxides or XeF2 .
报道了在三甲基甲硅烷基三氟甲磺酸酯（TMSOTf）存在下，双[（二烷基氨基）环丙烯亚胺]与二卤化膦反应形成二亚胺稳定的以P（III）为中心的双阳离子。通过X射线衍射分析确定了新化合物的结构，并通过电化学方法评估了它们作为配体的给体能力。尽管它们带有两个正电荷，但这些化合物表现出膦和亚磷酸酯之间的中间行为。还报道了L2PR部分与Au（I）和Ag（I）的配位。更令人惊讶的是，在过氧化物或XeF2等强氧化剂存在下，这些磷中心可以被氧化为相应的P（V）双阳离子。
