Crystal and Molecular Structure of an Eight-Coodinate <i>N</i>-Methyltetraphenylporphyrin Complex: Diacetato(<i>N</i>-methyl-<i>meso</i>-tetraphenylporphyrinato)thallium(III)

The crystal structure of diacetato(N-methyl-meso-tetraphenylporphyrinato)thallium(III), Tl(N-Me-tpp)(OAc)2 (1), was established, and the coordination sphere around the Tl3+ ion is described as an eight-coordinate square-based antiprism in which two cis chelating bidentate OAc- groups occupy two apical sites. The plane of the three pyrrole nitrogen atoms (i.e., N(1), N(3), N(4)) strongly bonded to Tl3+ is adopted as a reference plane 3N. The pyrrole N(2) ring bearing the methyl group (i.e., C(45)H3) is the most deviated one from the 3N plane, making a dihedral angle of 21.4°, whereas smaller angles of 9.1°, 7.1°, and 0.9° occur with pyrroles N(1), N(3), and N(4), respectively. Because of its larger size, the thallium(III) ion Tl3+ is considerably out of the 3N plane; its displacement of 1.17 Å is in the same direction as that of the two apical OAc- ligands. The intermolecular acetate exchange process for 1 in THF-d8 solvent is examined through 1H NMR temperature-dependent measurements. In the slow-exchange region, the methyl and carbonyl carbons of the OAc- groups in 1 are separately located at δ 18.6 [3J(Tl−13C) = 405 Hz] and 170.8 [2J(Tl−13C) = 334 Hz] at −80 °C, respectively.