提出了一种新的金属卟啉二聚体家族,其包含金属-金属(过渡-非过渡金属)键。用NaBH 4还原过渡金属卟啉配合物(Por)Rh III(Cl),生成低氧化态配合物(Por)Rh I- Na +,该低价态配合物通过与氯铟铟卟啉衍生物(Por)In III反应(Cl),产生了上述新家族。通过选择合适的卟啉配体,可以系统地改变这些二聚体的键稳定性。含铑-铟键的卟啉二聚体的合成及其在1的基础上的完整表征描述了1 H NMR,UV-可见光谱和FT-IR光谱。对这些配合物的光敏性的初步研究提供了有关金属-金属键稳定性的充分信息。
Action of alkyl halides on homo- and heteroporphyrin dimers involving a rhodium-indium bond, producing porphyrin complexes containing metal-carbon and metal-halide bonds
作者:D. Lux、D. Daphnomili、A.G. Coutsolelos
DOI:10.1016/s0277-5387(00)88149-8
日期:1994.8
The reactivity of the novel family of metalloporphyrin dimers containing a Rh-In bond towards alkyl halides is presented. The chemical reactivity of the homoleptic (same porphyrin ligand) and heteroleptic (different porphyrin ligand) porphyrin complexes with Rh-In metal-metal bond has been examined by photo- and thermal-processes in the presence of alkyl halides under anaerobic conditions in the dark. The photolytic and thermal reactions have been studied to define the polarity of the Rh-In single bond, as well as to identify the products. The presence of complexes containing Rh-C bonds in the reaction mixture detected by UV-vis spectroscopy postulated the formulation Rh(I)(-): --> In(III)(+) for the polarity of the metal-metal bond. In order to characterize the products we compare our spectroscopic results with those of the literature and those of authentic Rh-C containing complexes.