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Coupling Ferrocene To Brominated Tetraazaporphyrin: Exploring An Alternative Synthetic Pathway For Preparation Of Ferrocene-Containing Tetraazaporphyrins, Victor N. Nemykin, Elena A. Makarova, Nathan R. Erickson, Pavlo V. Solntsev

Turkish Journal of Chemistry

A Castro--Stephens coupling reaction between metal-free 3(2),8(7)-dibromo- 2(3),7(8),12(13),17(18)-tetra-tert-butyl-5,10,15,20-tetraazaporphyrin and (ferrocenylethynyl)copper resulted in the formation of copper 2(3),7(8),12(13), 17(18)-tetra-tert-butyl-3(2), 8(7)-di(ferrocenylethynyl)-5,10,15,20-tetraazaporphyrin and copper 2(3),7(8),12(13),17(18)-tetra-tert-butyl-3(2)-ferrocenylethynyl-5, 10,15,20-tetraazaporphyrin, which were separated in the form of 2 positional isomers along with copper 3(2)-bromo-2(3),7(8),12(13),17(18)-tetra-tert-butyl-5,10,15,20-tetraazaporphyrin and copper 2(3),7(8),12(13),17(18)-tetra-tert-butyl-5,10,15,20-tetraazaporphyrin. A similar reaction with metal-free 3(2),8(7),13(12), 18(17)-tetrabromo-2(3),7(8),12(13),17(18)-tetra-tert-butyl-5,10,15,20-tetraazaporphyrin resulted in only a trace amount of 3(2),8(7),13(12)-tribromo-2(3),7(8),12(13),17(18)-tetra-tert-butyl-18(17) -ferrocenylethynyl-5,10,15,20-tetraazaporphyrin, while no products with larger number of organometallic substituents were observed. Direct coupling between ferrocenelithium and 3(2),8(7)-dibromo-2(3),7(8),12(13),17(18)-tetra-tert-butyl-5,10,15,20-tetraazaporphyrin resulted in a debromination reaction accompanied by very minor dimerization of the tetraazaporphyrin core, which was explained based on the steric properties of the parent tetraazaporphyrin. The …