Electronic structure of transition metal-isocorrole complexes: a first quantum chemical study

B.F. van Oort, E. Tangen, A. Ghosh

Research output: Contribution to journalArticleAcademicpeer-review

24 Citations (Scopus)

Abstract

DFT calculations indicate that the broad electronic-structural features of metalloisocorroles are rather similar to those of analogous metallocorroles. Thus, like their corrole analogues, many metalloisocorroles feature substantially non-innocent ligands. Another key point is that both corroles and isocorroles can exhibit at least two kinds of radical character, a2 and b1. However, corrole and isocorrole derivatives also differ significantly in a few ways: for example, the S = 1/2 CoPh complexes of corrole and isocorrole exhibit ground states of different symmetries (2A and 2A, respectively, in Cs notation), reflecting different interplays of metal(d)-ligand(p) interactions in corrole versus isocorrole derivatives. The ligand non-innocence phenomena encountered in this study are broadly reminiscent of similar phenomena in peroxidase compound I intermediates and their synthetic models. It seems reasonable, therefore, to adopt the view that this study, along with related studies on corrole derivatives, provides a broader chemical context for appreciating the electronic structures of high-valent heme protein intermediates.
Original languageEnglish
Pages (from-to)2442-2445
Number of pages4
JournalEuropean Journal of Inorganic Chemistry
Volume2004
Issue number12
DOIs
Publication statusPublished - 2004

Keywords

  • peroxidase compound-i
  • pi-cation radicals
  • noninnocent ligands
  • porphyrins
  • corroles
  • centers
  • iron(iv)
  • electrochemistry
  • absorption
  • insights

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