Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34/36, 14195 Berlin, Germany.
Dalton Trans. 2018 Jul 17;47(28):9355-9366. doi: 10.1039/c8dt01441h.
A series of substituted, pyridyl-functionalized 2,4,6-triarylpyrylium salts were prepared and investigated for their light absorption and emission properties. After reaction with P(SiMe3)3, the corresponding λ3-phosphinines were obtained, which carry on the 4- or 6-aryl ring ±I and ±M substituents. Supported by DFT calculations, a systematic evaluation of the σ-donor and π-donor as well as π-acceptor properties of these low-coordinate P,N-hybrid ligands was performed. The modular synthetic approach allowed us at the same time to synthesize the structurally related bipyridine derivatives for comparison reasons. Reaction of the chelating ligands with [W(CO)6] in THF afforded the corresponding [(P^N)W(CO)4] and [(N^N)W(CO)4] complexes. A crystallographic characterization of selected coordination compounds revealed significant structural differences between the pyridyl-phosphinine- and the bipyridine-based compounds. Their characterization by means of IR-spectroscopy gave experimental insight into the electronic properties of the respective ligands.
一系列取代的、吡啶基功能化的 2,4,6-三芳基吡喃鎓盐被制备出来，并研究了它们的光吸收和发光性质。与 P(SiMe3)3 反应后，得到了相应的 λ3-膦，它们在 4-或 6-芳环上带有 ±I 和 ±M 取代基。通过 DFT 计算的支持，对这些低配位的 P,N-杂化配体的 σ-给体和 π-给体以及 π-受体性质进行了系统的评估。模块化的合成方法使我们能够同时合成结构相关的联吡啶衍生物，以便进行比较。螯合配体与 [W(CO)6] 在 THF 中的反应得到了相应的 [(P^N)W(CO)4] 和 [(N^N)W(CO)4] 配合物。对所选配合物的晶体学表征揭示了基于吡啶基膦和联吡啶基化合物之间的显著结构差异。通过红外光谱法对它们的表征，为各配体的电子性质提供了实验上的了解。
