Syntheses and structures of thiophosphorylatocavitands and their reactivity towards first-row transition metal halides

Two-step reactions of resorcin[4]arene (1) or methylresorcin[4]arene (2) with PPhCl2 and subsequent in situ oxidation with sulfur powder afforded a series of new thiophosphorylatocavitands 1a–1d or 2a–2d, respectively. Molecular structures of 1a⋅C3H6O, 1d⋅C3H6O⋅CH4O, 2a⋅2C2H6O⋅2H2O, and 2b⋅2C4H8O have been determined by X-ray diffraction analysis, which showed the C4v stereoisomer with the four P = S bonds oriented towards the molecular cavity. The binding ability of thiophosphorylatocavitands 1a and 2b towards Cu(I), Mn(II), Co(II), Cu(II), and Zn(II) halides was studied by UV/vis absorption.