A siloxyl bis-pocket thiolate-Tailed Fe(III) porphyrin complex

Ming Fang, Scott R. Wilson, Kenneth S. Suslick

Research output: Contribution to journalArticlepeer-review

Abstract

We report the synthesis and characterization of a bis-pocket iron(III) porphyrin complex that has a covalently attached siloxy thiolate group as the axial ligand. As a new cytochrome P450 model compound, this siloxyl bis-pocket thiolate-Tailed iron(III) porphyrin is easily synthesized and is surprisingly stable under air due to the extreme steric protection of the siloxy pockets on both faces of the porphyrin. A single-crystal XRD structure has been determined; the Fe-S bond distance is 2.237 (7) Å with Fe-N bond distances of 2.100 (8) and the Fe is 0.5 Å out of the mean porphyrin plane. The Fe-S bond distance in the siloxy thiolate-Tailed iron(III) porphyrin is very similar to that in cytochrome P450 and this structure represents a very rare crystallographically-characterized five-coordinate high spin alkylthiolate-Tailed ferric porphyrin. EPR spectrum of this compound showed g values and an E/D ratio very similar to those of cytochrome P450 (CYP450) enzyme, demonstrating the importance of using a very basic thiolate group as the axial ligand in P450 model studies. UV-vis studies of its reduced form with carbon monoxide shows a hyper spectrum, which is characteristic of carbonyl complexes of Fe(II)porphyrin thiolates.

Original languageEnglish (US)
Pages (from-to)790-795
Number of pages6
JournalJournal of Porphyrins and Phthalocyanines
Volume21
Issue number12
DOIs
StatePublished - Dec 1 2017

Keywords

  • EPR
  • XRD
  • bis-pocket porphyrin
  • cytochrome P450
  • iron porphyrinate
  • iron(III)-Thiolate

ASJC Scopus subject areas

  • Chemistry(all)

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