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

• Published in: Journal of organic chemistry Vol. 75; no. 5; pp. 1534 - 1549
• Main Authors: Suijkerbuijk, Bart M. J. M, Tooke, Duncan M, Lutz, Martin, Spek, Anthony L, Jenneskens, Leonardus W, van Koten, Gerard, Klein Gebbink, Robertus J. M
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 05.03.2010; Amer Chemical Soc
• Subjects: Catalysis; Chemistry; Chemistry, Organic; Chimera; Crystallography, X-Ray; Electrochemistry; Electronics; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings; Ligands; Metalloporphyrins - chemical synthesis; Metalloporphyrins - chemistry; Metals - chemistry; Molecular Structure; Organic chemistry; Oxidation-Reduction; Physical Sciences; Preparations and properties; Science & Technology; MOLECULAR-STRUCTURE; CRYSTAL-STRUCTURE; BUILDING-BLOCKS; AXIAL COORDINATION; PINCER COMPLEXES; PERIPHERALLY-METALATED PORPHYRINS; PLATINUM; SINGLET OXYGEN; PARASUBSTITUTED TETRAPHENYLPORPHYRIN; FREE-BASE; Intramolecular reaction; Ligand binding; Stepwise mechanism; Metal Ions; Metal complex; Metalation; Oxidation; Metalloporphyrin; Selectivity; Chemical synthesis; Porphyrin derivatives; Metal Complexes
• ISSN: 0022-3263; 1520-6904
• 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.