Rhenium-imido Corroles

Metallocorroles involving Sd transition metals are currently of interest as near-IR phosphors and as photosensitizers for oxygen sensing and photodynamic therapy. Their syntheses, however, are often bedeviled by capricious and low-yielding protocols. Against this backdrop, we describe rhenium-imido corroles, a new class of Sd metallocorroles, synthesized simply and in respectable (similar to 30%) yields via the interaction of a free-base corrole, Re-2(C0)(10), K2CO3, and aniline in 1,2,4-trichlorobenzene at -190 degrees C in a sealed vial under strict anaerobic conditions. The generality of the method was shown by the synthesis of six derivatives, including those derived from meso-tris(pentafluorophenyl)corrole, H-3[TPFPC], and five different mesotris(p-X-phenyl)corroles, H-3[TpXPC], where X = CF3, F, H, CH3, OCH3. Single-crystal X-ray structures obtained for two of the complexes, Re[TpFPC](NPh) and Re[TpCF(3)PC](NPh), revealed relatively unstrained equatorial Re-N distances of similar to 2.00 angstrom, a similar to 0.7-angstrom displacement of the Re from the mean plane of the corrole nitrogens, and an Re-N-imido distance of similar to 1.72 angstrom. Details of the corrole skeletal bond distances, diamagnetic H-1 NMR spectra, relatively substituent-independent Soret maxima, and electrochemical HOMO-LUMO gaps of similar to 2.2 V all indicated an innocent corrole macrocycle. Surprisingly, unlike several other classes of Sd metallocorroles, the Re-imido complexes proved nonemissive in solution at room temperature and also failed to sensitize singlet oxygen formation, indicating rapid radiationless deactivation of the triplet state, presumably via the rapidly rotating axial phenyl group. By analogy with other metal-oxo and -imido corroles, we remain hopeful that the Re-imido group will prove amenable to further elaboration and thereby contribute to the development of a somewhat challenging area of coordination chemistry.