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• W1989777773 abstract "Several new complexes of organotin(IV) moieties with MCln[meso-tetra(4-sulfonatophenyl)porphine], (R2Sn)2MCln[meso-tetra(4-sulfonatophenyl)-porphinate]s and (R3Sn)4MCln [meso-tetra(4-sulfonatophenyl)porphinate]s, [M = Fe(III), Mn(III): n = 1, R = Me, n-Bu; Ph; M = Sn(IV): n = 2, R = Me, n-Bu] have been synthesized and their solid state configuration investigated by infrared (IR) and Mössbauer spectroscopy, and by 1H and 13C NMR in D2O. The electron density on the metal ion coordinated inside the porphyrin ring is not influenced by the organotin(IV) moieties bonded to the oxygen atoms of the side chain sulfonatophenyl groups, as it has been inferred on the basis of Mössbauer spectroscopy and, in particular, from the invariance of the isomer shift of the Fe(III) and Sn(IV) atoms coordinated into the porphyrin square plane of the newly synthesized complexes, with respect to the same atoms in the free ligand. As far as the coordination polyhedra around the peripheral tin atoms are concerned, infrared spectra and experimental Mössbauer data would suggest octahedral and trigonal bipyramidal environments around tin, in polymeric configurations obtained, respectively, in the diorganotin derivatives through chelating or bridging sulfonate groups coordinating in the square plane, and in triorganotin(IV) complexes through bridging sulfonate oxygen atoms in axial positions. The structures of the (Me3Sn)4Sn(IV)Cl2[meso-tetra(4-sulfonatophenyl)porphinate] and of the two model systems, Me3Sn(PS)(HPS) and Me2Sn(PS)2 [HPS = phenylsulfonic acid], have been studied by a two layer ONIOM method, using the hybrid DFT B3LYP functional for the higher layer, including the significant tin environment. This approach allowed us to support the structural hypotheses inferred by the IR and Mössbauer spectroscopy analysis and to obtain detailed geometrical information of the tin environment in the compounds investigated. 1H and 13C NMR data suggested retention of the geometry around the tin(IV) atom in D2O solution." @default.
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• W1989777773 date "2006-04-01" @default.
• W1989777773 modified "2023-10-14" @default.
• W1989777773 title "Structural investigations on diorgano- and triorganotin(IV) derivatives of [meso-tetra(4-sulfonatophenyl)porphine] metal chlorides" @default.
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• W1989777773 doi "https://doi.org/10.1016/j.jorganchem.2005.12.012" @default.
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