A new synthesis of acetato porphyrinato indium(III) from indium(III) oxide and X-ray crystal structures of in(tpyp)(OAc) and in(tmpp)(OAc)

Article abstract of DOI:10.1016/0277-5387(95)00541-2

The indium porphyrin complexes [In(tpp)(OAc), In(tpyp)(OAc), In(tmpp) (OAc)] were prepared in good yields by refluxing the respective porphyrin (tpp, tpyp, tmpp) with In₂O₃ in acetic acid containing sodium acetate. The structures of In(tpyp) (OAc) and In(tmpp)(OAc) were determined by a single-crystal X-ray structure analysis. The indium atom is displaced 0.731 A from the mean porphyrin plane (C₂₀N₄). The geometry around the indium centre of the In(tpyp)(OAc) molecule has In(1) - O(1) = 2.185(6), In(1) - O(2) = 2.412(6) and average In(1) - N_p = 2.177(5) A. This indicates that an asymmetric-bidentate acetato group is coordinated to the indium(III) atom in In(tpyp)(OAc). In the structure of In(tmpp)(OAc) the indium(1)-oxygen distances are In(1) - O(6) = 2.31(1) and In(1) - O(5) = 2.31(1) A, whereas the indium(1) atom lies 0.697 and 0.758 A from the four porphyrin nitrogens (4 N_p) and the 24-atom porphyrin plane (C₂₀N₄), respectively. This indicates that In(1)(tmpp)(OAc) contains a symmetric bidentate binding of the acetate ligand. Copyright