Watt Fabian A, McCabe Karl N, Schoch Roland, Maron Laurent, Hohloch Stephan
Paderborn University, Warburger Straße 100, 33098 Paderborn, Germany.
Chem Commun (Camb). 2020 Dec 21;56(98):15410-15413. doi: 10.1039/d0cc06670b. Epub 2020 Nov 25.
Deprotonation of the terminal phosphido complex (PN)La(PHMes) (1) results in the C-H-activation of one of the PN ligands, formally retaining the PHMes group. The reaction mechanism and the possible involvement of the transient phosphinidene complex 2 are investigated by theoretical and chemical means including a deuteration experiment employing (PN)La(PDMes) (1-d). Furthermore, the thermal stability of product [K(2.2.2-cryptand)][(PN)(PN)La(PHMes)] (3b) is examined, giving the diphosphido complex [K(2.2.2-cryptand)][(PN)La(PMes)] (6).
末端磷化物配合物(PN)La(PHMes) (1)的去质子化导致其中一个PN配体发生C-H活化，形式上保留了PHMes基团。通过理论和化学方法，包括使用(PN)La(PDMes) (1-d)的氘代实验，研究了反应机理以及瞬态磷烯配合物2可能的参与情况。此外，还研究了产物[K(2.2.2-穴醚)][(PN)(PN)La(PHMes)] (3b)的热稳定性，得到了二磷化物配合物[K(2.2.2-穴醚)][(PN)La(PMes)] (6)。
