Organic Chemistry & Catalysis, Debye Institute for Nanomaterials Science, Faculty of Science, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands.
J Org Chem. 2010 Mar 5;75(5):1534-49. doi: 10.1021/jo902402g.
Several heteromultimetallic pincer-porphyrin hybrids have been prepared in excellent yields by stepwise metalation of a general precursor, [2H(Br(NCN))(4)], which was designed in such a way so as to guarantee selectivity for either the porphyrin or pincer sites during the metalation steps. First, a metal was introduced in the porphyrin cavity using a metal(II) salt, followed by metalation of the pincer units through oxidative addition to an appropriate metal(0) complex. The resulting multimetallic complexes show an appreciable amount of intramolecular communication between the meso-pincer metal groups and the central metalloporphyrin component. This was manifested in changes of the optical and ligand-binding properties of the metalloporphyrin part upon reactions at the peripheral pincer sites.
几种异多核卟啉钳形配合物已通过逐步金属化通用前体[2H(Br(NCN))(4)]以极好的产率制备，该前体的设计方式可在金属化步骤中保证卟啉或钳形部位的选择性。首先，使用金属(II)盐将金属引入卟啉腔中，然后通过氧化加成将金属化引入适当的金属(0)配合物中。所得的多金属配合物在介孔钳形金属基团和中心金属卟啉组分之间表现出相当大的分子内通信。这表现在配体结合性质的变化上，在卟啉部分的外围钳形部位反应时，光学和配位。
