The size mismatch between the large ionic radii of low-oxidation-state 5d ions and the contracted N4 cores of corroles makes the synthesis of 5d metallocorroles a challenging arena for the coordination chemist's art (Thomas, K. E.; Alemayehu, A. B.; Conradie, J.; Beavers, C. M.; Ghosh, A. Acc. Chem. Res. 2012  , 45, 1203�1214). A recent, success in this area has been the synthesis of gold(III) corroles. Platinum corroles, by contrast, have resisted synthesis, remaining the Holy Grail of corrole chemistry. In our hands, a rather accidental, oxidative metallation protocol has now led to six-coordinate Pt(IV) corroles, which could be oxidized to surprisingly stable 'p-cation radical' derivatives PtIV(Cor�)ArAr'. Several of these latter complexes proved amenable to single-crystal X-ray analysis, as depicted by the following representative thermal ellipsoid plot. These oxidized complexes exhibit strongly substituent-sensitive electronic absorption spectra embodying clear signatures of their noninnocent nature.

Geometric and electronic structure of platinum corroles: Excited-state signatures of ligand noninnocence

248th National Meeting (2014)

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