Synthesis and atructure of [meso-triarylcorrolato]silver(III)

Christian Brückner; Cheri A Barta; Raymond P Briñas; Jeanette A Krause Bauer

doi:10.1021/ic0261171

Synthesis and atructure of [meso-triarylcorrolato]silver(III)

Inorg Chem. 2003 Mar 10;42(5):1673-80. doi: 10.1021/ic0261171.

Authors

Christian Brückner¹, Cheri A Barta, Raymond P Briñas, Jeanette A Krause Bauer

Affiliation

¹ Department of Chemistry, Unit 3060, University of Connecticut, Storrs 06269-3060, USA. [email protected]

PMID: 12611538
DOI: 10.1021/ic0261171

Abstract

An efficient meso-triarylcorrole synthesis is detailed, and the formation and spectroscopic properties of their diamagnetic square-planar d(8) 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 TTCAg(III), as its toluene solvate (crystal data for C(40)H(29)N(4)Ag.C(7)H(8): monoclinic space group C2/c with a = 21.4679(19) A, b = 20.7606(19) A, c = 16.0122(11) A, beta = 93.700(4) degrees, V = 7121.5(10) A(3), Z = 8, R = 0.0453, and R(w) = 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.