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 Solntsev

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

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-tetraazaporphy-rin, while no products with larger number of organometallic substituents were observed. Direct coupling between fer-rocenelithium 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 target compounds were characterized using APCI mass spectrometry, UV-vis, and MCD spectroscopy, while the electronic structure of ferrocenylethyl-containing products was predicted by DFT approach. X-ray structures of individual positional isomers of copper 2-bromo-3,7,12,18-tetra-tert-butyl-5,10,15,20-tetraazaporphyrin and 3, 7, 12,18-tetrabromo-2,8,13,17-tetra-tert-butyl-5,10,15,20-tetraazaporphyrin were also discussed.

Original languageEnglish (US)
Pages (from-to)1027-1045
Number of pages19
JournalTurkish Journal of Chemistry
Volume38
Issue number6
DOIs
StatePublished - 2014

Bibliographical note

Publisher Copyright:
© 2014 TÜB̄TAK.

Keywords

  • Coupling reaction
  • Density functional theory
  • Ferrocene
  • Magnetic circular dichroism
  • Tetraazaporphyrin
  • UV-vis spectra

Fingerprint Dive into the research topics of 'Coupling ferrocene to brominated tetraazaporphyrin: Exploring an alternative synthetic pathway for preparation of ferrocene-containing tetraazaporphyrins'. Together they form a unique fingerprint.

Cite this