Electronic structure of bis(imino)pyridine iron dichloride, monochloride, and neutral ligand complexes: A combined structural, spectroscopic, and computational study

Suzanne C. Bart, Krzysztof Chłopek, Eckhard Bill, Marco W. Bouwkamp, Emil Lobkovsky, Frank Neese, Karl Wieghardt, Paul J. Chirik

Research output: Contribution to journalArticle

381 Scopus citations

Abstract

The electronic structure of a family of bis(imino)pyridine iron dihalide, monohalide, and neutral ligand compounds has been investigated by spectroscopic and computational methods. The metrical parameters combined with Mössbauer spectroscopic and magnetic data for (iPrPDI)FeCl2 ( iPrPDI = 2,6-(2,6-iPr2C6H 3N=CMe)2C5H3N) established a high-spin ferrous center ligated by a neutral bis(imino)pyridine ligand. Comparing these data to those for the single electron reduction product, ( iPrPDI)FeCl, again demonstrated a high-spin ferrous ion, but in this case the SFe = 2 metal center is antiferromagnetically coupled to a ligand-centered radical (SL = 1/2), accounting for the experimentally observed S = 3/2 ground state. Continued reduction to (iPrPDI) FeLn (L = N2, n = 1,2; CO, n = 2; 4-(N,N-dimethylamino) pyridine, n = 1) resulted in a doubly reduced bis(imino)pyridine diradical, preserving the ferrous ion. Both the computational and the experimental data for the N,N-(dimethylamino)pyridine compound demonstrate nearly isoenergetic singlet (SL = 0) and triplet (SL = 1) forms of the bis(imino)pyridine dianion. In both spin states, the iron is intermediate spin (SFe = 1) ferrous. Experimentally, the compound has a spin singlet ground state (S = 0) due to antiferromagnetic coupling of iron and the ligand triplet state. Mixing of the singlet diradical excited state with the triplet ground state of the ligand via spin-orbit coupling results in temperature-independent paramagnetism and accounts for the large dispersion in 1H NMR chemical shifts observed for the in-plane protons on the chelate. Overall, these studies establish that reduction of ( iPrPDI)FeCl2 with alkali metal or borohydride reagents results in sequential electron transfers to the conjugated π-system of the ligand rather than to the metal center.

Original languageEnglish (US)
Pages (from-to)13901-13912
Number of pages12
JournalJournal of the American Chemical Society
Volume128
Issue number42
DOIs
StatePublished - Oct 25 2006
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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