Synthesis of 'Skewered Complexes':Reaction of Rhenium Carbonyl Porphyrin Complexes with Antimony Pentachloride.

摘要

The Synthesis of the first 'skewered' porphyrin complex is reported. Oxidative chlorination of rhenium carbonylporphyrin complexes by antimony pentachloride provides the first reported examples where out-of-plane metalloporphyrins react in a manner similar to cyclopentadienyl metal carbonyl complexes. From the reaction of a 1:4 or 1:2 mole ration of bis(tricarbonylrhenium)-mu-tetraphenylporphyrin and antimony pentachloride, the corresponding salts ((Re(CO)3Cl)2TPP.2SbCl6 or (Re(CO)3)(Re(CO)3)(Re(CO)3Cl)TPP.SbCl6), respectively, were obtained in good yields. A third product (Re(CO)3)2(TPP.SbCl6) was also obtained. A X-ray structure determination on this compound was carried out. The monocationic metalloporphyrin has a similar structure to that found for the starting compound. However, in this case the M-M distance of 2.95 A indicates a probably metal-metal bond of bond-order 1/2 through the porphyrin 'core'. (Author)