Zhang Yuehong, Cao Wei, Wang Kang, Jiang Jianzhuang
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China.
Dalton Trans. 2014 Jun 28;43(24):9152-7. doi: 10.1039/c4dt00216d.
Reaction of metal-free N-confused 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin (H2NTClPP) with metal-free 5,10,15,20-tetrakis[(4-tert-butyl)phenyl]porphyrin (H2TBPP) in the presence of M(III)(acac)3·nH2O (acac = acetylacetonate) in refluxing 1,2,4-trichlorobenzene (TCB) led to the isolation of heteroleptic bis(porphyrinato) rare earth compounds M(III)(HNTClPP)(TBPP) (M = La, Pr) (1, 2) in 6.7-10% yield. These represent the first examples of sandwich-type porphyrin rare earth double-decker complexes that involve N-confused porphyrin ligand. Different from their homoleptic bis(porphyrinato) rare earth double-decker counterparts HM(III)(TBPP)2 (M = La, Pr) (3, 4), the acidic proton in the heteroleptic analogues was revealed to localize at the inverted pyrrole nitrogen atom of the N-confused porphyrin ligand on the basis of NMR spectroscopic studies. Nevertheless, their heteroleptic bis(porphyrinato) sandwich molecular nature was confirmed on the basis of single crystal X-ray diffraction analysis over the praseodymium double-decker complex.
在回流的1,2,4-三氯苯（TCB）中，无金属的N-稠合5,10,15,20-四（4-氯苯基）卟啉（H2NTClPP）与无金属的5,10,15,20-四[（4-叔丁基）苯基]卟啉（H2TBPP）在M(III)(acac)3·nH2O（acac = 乙酰丙酮）存在下反应，以6.7 - 10%的产率分离得到杂配双（卟啉基）稀土化合物M(III)(HNTClPP)(TBPP)（M = La，Pr）（1, 2）。这些是涉及N-稠合卟啉配体的夹心型卟啉稀土双层配合物的首例。与它们的同配双（卟啉基）稀土双层类似物HM(III)(TBPP)2（M = La，Pr）（3, 4）不同，基于核磁共振光谱研究，杂配类似物中的酸性质子定位于N-稠合卟啉配体的倒转吡咯氮原子上。然而，基于对镨双层配合物的单晶X射线衍射分析，证实了它们的杂配双（卟啉基）夹心分子性质。
