Synthesis and Structure of [<i>m</i><i>eso</i>-Triarylcorrolato]silver(III)

An efficient meso-triarylcorrole synthesis is detailed, and the formation and spectroscopic properties of their diamagnetic square-planar d8 Ag(III) complexes are described. The spectroscopic properties of the [corrolato]Ag(III) complexes are contrasted with those of the corresponding [porphyrinato]Ag(II) complexes. The oxidation state of the central metal in the corrolato complexes was inferred from their diamagnetic NMR spectra, from X-ray photoelectron spectroscopy measurements, and by single-crystal X-ray diffractometry of the [meso-tetra-p-tolylcorrolato]silver(III) complex TTCAgIII, as its toluene solvate (crystal data for C40H29N4Ag·C7H8: monoclinic space group C2/c with a = 21.4679(19) Å, b = 20.7606(19) Å, c = 16.0122(11) Å, β = 93.700(4)°, V = 7121.5(10) Å3, Z = 8, R = 0.0453, and Rw = 0.1131). The conformation of the corrolato ligand in the complex is slightly saddled. The Ag(III) complexes are without precedent in the coordination chemistry of corroles. The Ag(III) complexes underline the ability of meso-triarylcorroles to stabilize higher oxidation states as compared to the corresponding meso-tetraarylporphyrinato complexes.