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)

The indium porphyrin complexes [In(tpp)(OAc), In(tpyp)(OAc), In(tmpp) (OAc)] were prepared in good yields by refluxing the respective porphy rin (tpp, tpyp, tmpp) with In2O3 in acetic acid containing sodium acet ate. The structures of In(tpyp) (OAc) and In(tmpp)(OAc) were determine d by a single-crystal X-ray structure analysis. The indium atom is dis placed 0.731 Angstrom from the mean porphyrin plane (C20N4). The geome try 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) Angstrom. This indicates that an asymmetric-bidentate acetato group i s coordinated to the indium(III) atom in In(tpyp)(OAc). In the structu re of In(tmpp)(OAc) the indium(1)-oxygen distances are In(1)-O(6)= 2.3 1(1) and In(1)-O(5) = 2.31(1) Angstrom, whereas the indium(1) atom lie s 0.697 and 0.758 Angstrom from the four porphyrin nitrogens (4 N-p) a nd the 24-atom porphyrin plane (C20N4), respectively. This indicates t hat In(1)(tmpp)(OAc) contains a symmetric bidentate binding of the ace tate ligand. Copyright (C) 1996 Elsevier Science Ltd.