Synthesis of and Evidence for Electronic Communication within Heteromultimetallic Tetrakis(NCN-pincer metal)−(Metallo)porphyrin Hybrids

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• 作者：Bart M. J. M. Suijkerbuijk ; Duncan M. Tooke ; Martin Lutz ; Anthony L. Spek ; Leonardus W. Jenneskens ; Gerard van Koten ; Robertus J. M. Klein Gebbink
• 刊名：Journal of Organic Chemistry
• 出版年：2010
• 出版时间：March 5, 2010
• 年：2010
• 卷：75
• 期：5
• 页码：1534-1549
• 全文大小：1216K
• 年卷期：v.75,no.5(March 5, 2010)
• ISSN：1520-6904

文摘

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.