Structural investigations on diorgano- and triorganotin(IV) derivatives of [meso-tetra(4-sulfonatophenyl)porphine]metal chlorides.

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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 Mo¨ ssbauerspectroscopy, 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 tothe oxygen atoms of the side chain sulfonatophenyl groups, as it has been inferred on the basis of Mo¨ssbauer 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 newlysynthesized 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 Mo¨ssbauerdata would suggest octahedral and trigonal bipyramidal environments around tin, in polymeric configurations obtained, respectively, inthe 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 functionalfor the higher layer, including the significant tin environment. This approach allowed us to support the structural hypothesesinferred by the IR and Mo¨ssbauer spectroscopy analysis and to obtain detailed geometrical information of the tin environment inthe compounds investigated.1H and 13C NMR data suggested retention of the geometry around the tin(IV) atom in D2O solution.
Lingua originaleEnglish
pagine (da-a)1573-1583
Numero di pagine11
RivistaJournal of Organometallic Chemistry
Stato di pubblicazionePublished - 2006

All Science Journal Classification (ASJC) codes

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  • ???subjectarea.asjc.1600.1606???
  • ???subjectarea.asjc.1600.1605???
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