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• W2073676213 abstract "The hydrolysis of the monomeric five-coordinate (2-BzO-TPP)MnIIICl complex has been investigated.1 Evidence for the formation of the cyclic trimeric complex [(2-O−TPP)MnIII]3 is presented. The 1H NMR spectroscopic evidence indicates that the trimeric manganese(III) complex has a head-to-tail cyclic trimeric structure with the pyrrolic alkoxide groups forming bridges from one macrocycle to the manganese(III) ion in the adjacent macrocycle PMn−O−PMn−O−PMn−O. The three manganese(III) porphyrin subunits are not equivalent. The characteristic upfield shift of the 3-H pyrrole resonance (−111.5 ppm at 291 K) was determined and considered as the diagnostic feature for the high-spin d4 manganese(III)−pyrrole alkoxide coordination. The strong upfield shift of the 3-H resonance has been accounted for by the donation of the electron density from the filled orbital of the 2-O atom on the half-occupied dz2 orbital of the external manganese(III) ion. The other pyrrole resonances produce the complex multiplet at the typical −5 to −40 ppm region. The 1H NMR spectra of the series of monomeric 2-substituted manganese(III) 5,10,15,20-tetraphenylporphyrin complexes (2-X-TPP)MnIIICl have been obtained and analyzed. The pattern of the assigned seven pyrrole resonances reflects the asymmetry imposed by 2-substitution and has been used as a 1H NMR spectroscopic probe to map the spin density distribution. The electronic effect is strongly localized at the β-substituted pyrrole. The upfield shift of the 3-H resonance increases in the order (2-NO2-TPP)MnIIICl < (2-BzO-TPP)MnIIICl < (2-OCH3-TPP)MnIIICl < (2-OH-TPP)MnIIICl < (2-NH2-TPP)MnIIICl < [(2-O-TPP)MnIII(OH)]- following the increasing electron-donating properties of the β-substituent." @default.
• W2073676213 created "2016-06-24" @default.
• W2073676213 creator A5054127173 @default.
• W2073676213 creator A5076956048 @default.
• W2073676213 date "1996-01-01" @default.
• W2073676213 modified "2023-09-23" @default.
• W2073676213 title "Monomeric and Trimeric Manganese(III) Complexes of 2-Hydroxy-5,10,15,20-tetraphenylporphyrin. Synthesis and Characterization" @default.
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• W2073676213 doi "https://doi.org/10.1021/ic951663y" @default.
• W2073676213 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/11666680" @default.
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