Synthesis, spectral and molecular studies of half-sandwich arene ruthenium and Cp*Rh/Cp*Ir complexes containing bidentate P-N and E-N ligands (E = S, Se) based on diphenyl (2-pyridyl)phosphine

摘要

The chalcogenide ligands {E=PPh2Py} (E = O, S, Se) were prepared by direct oxidation of diphenyl (2-pyridyl)phosphine using H2O2, S, and Se powder, respectively. The reaction of ligand with starting metal precursors [(arene)RuCl2](2) {M = Ru, arene = benzene; p-cymene} and [Cp*MCl2](2) (M = Rh, Ir) afforded a series of cationic half-sandwich complexes, [(arene/Cp*) MCl{kappa(2)-(NE)-EPPh2Py)}](+). Reaction of O=PPh2Py with precursors yielded known complexes [(arene/Cp*)MCl {kappa(2)-(PN)-PPh2Py)}](+) instead of expected complexes [(arene/Cp*)MCl{kappa(2)-(NO)-O=PPh2Py)}](+). All new complexes were isolated as PF6- counterion and characterized by spectroscopic techniques like FT-IR, NMR, mass, and UV-vis. Some representative complexes were structurally determined by X-ray crystallographic analysis, revealing typical three-legged piano stool geometry around the metal center with a five-membered metallacycle.