Metal Complexes of N-p-Nitrobenzoylamido- meso-tetraphenylporphyrin: cis-Acetato-N-p-nitrobenzoylimido-meso- tetraphenylporphyrinatothallium(III) and N-p-Nitrobenzoylimido-meso- tetraphenylporphyrinatonickel(II)

Metalloporphyrins with a bridged structure between the central metal and one of the four pyrrole nitrogens have drawn much attention in recent times. Bridged metalloporphyrins with only metal -NTs-N linkages (metal ) Zn,1 Ni,2 Fe,3 Hg,4 Ga,5 Tl,5 Ts) tosyl) have so far been reported. Callot et al. 2 reported the synthesis and1H NMR investigation of the metalation of N-p-nitrobenzoylamidomeso-tetraphenylporphyrin [ N-pHNCOC6H4NO2-Htpp] (tpp) dianion ofmeso-tetraphenylporphyrin) leading to mononuclear complexes of N-p-nitrobenzoylimido-meso-tetraphenylporphyrinatonickel(II) Ni( N-pNCOC6H4NO2-tpp) (1) and N-p-nitrobenzoylimidomesotetraphenylporphyrinatocopper(II) Cu( N-p-NCOC6H4NO2-tpp) (2). There are no X-ray structural data available for the metal ion [M(II) and M(III)] complexes of HNCOC6H4NO2-Htpp. In this paper, we report the X-ray structural determination of the title compound Ni( N-p-NCOC6H4NO2-tpp) (1), and we also present the results upon replacing Ni(II) with Tl(III) in 1 forming a new compound ( 3). This replacement increases the coodination number (CN) from 4 for1 to 6 for cis-acetatoN-p-nitrobenzoylimido-meso-tetraphenylporphyrinatothallium(III) Tl( N-pNCOC6H4NO2-tpp)(OAc) (3). The presence of acetate ligands in 3 plays a role in somewhat artificially increasing the coordination number. Because of the larger size of the Tl 3+ (r ion ) 1.025 Å),6 the relative position of OAc andp-nitrobenzoyl (NB) group coordinated to the Tl atom might lead to a cis configuration in3. In addition, the acetato exchange of Tl( NNTs-tpp)(OAc) observed in CD 2Cl2 prompted us to investigate a similar intermolecular exchange for complex 3 in THF-d8 by 1H and13C dynamic NMR method. 5