Synthesis and structure of 16 pi porphyrin metal complexes

Abstract

Recently, we obtained novel oxidized 16pi octaethyltetraphynylporphyrin(OETPP) and octaisobutyltetraphenylporphyrin(OiBTPP) by the reaction of OETPPLi2 or OiBTPPLi2 with SOCl2. These were the first characterized 16pi porphyrin, although in 2006, Vaid and coworkers also prepared [Li(TPP)][BF4] bearing 16pi porphyrin skeleton by the reaction of Li2(TPP) with thianthrenium tetrafluoroborate (Thn+BF4-). However 16pi porphyrin metal complex was not reported except for [Li(TPP)][BF4]. We report here synthesis and structure of the novel OiBTPPZnCl(ZnCl3) bearing 16pi porphyrin skeleton. The X-ray structure of OiBTPPZnCl(ZnCl3) shows very clear bond alternation and is much more distoreted from the mean plane of porphyrin core than that of OiBTPPZn(H2O).