EPR, ENDOR, and electronic structure studies of the Jahn-Teller distortion in an FeV nitride

George E. Cutsail, Benjamin W. Stein, Deepak Subedi, Jeremy M. Smith*, Martin L. Kirk, Brian M. Hoffman

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

41 Scopus citations


The recently synthesized and isolated low-coordinate FeV nitride complex has numerous implications as a model for high-oxidation states in biological and industrial systems. The trigonal [PhB(tBuIm) 3FeV≡N]+ (where (PhB(tBuIm) 3- = phenyltris(3-tert-butylimidazol-2-ylidene)), (1) low-spin d3 (S = 1/2) coordination compound is subject to a Jahn-Teller (JT) distortion of its doubly degenerate 2E ground state. The electronic structure of this complex is analyzed by a combination of extended versions of the formal two-orbital pseudo Jahn-Teller (PJT) treatment and of quantum chemical computations of the PJT effect. The formal treatment is extended to incorporate mixing of the two e orbital doublets (30%) that results from a lowering of the idealized molecular symmetry from D3h to C3v through strong "doming" of the Fe-C3 core. Correspondingly we introduce novel DFT/CASSCF computational methods in the computation of electronic structure, which reveal a quadratic JT distortion and significant e-e mixing, thus reaching a new level of synergism between computational and formal treatments. Hyperfine and quadrupole tensors are obtained by pulsed 35 GHz ENDOR measurements for the 14/15N-nitride and the 11B axial ligands, and spectra are obtained from the imidazole-2-ylidene 13C atoms that are not bound to Fe. Analysis of the nitride ENDOR tensors surprisingly reveals an essentially spherical nitride trianion bound to Fe, with negative spin density and minimal charge density anisotropy. The four-coordinate 11B, as expected, exhibits negligible bonding to Fe. A detailed analysis of the frontier orbitals provided by the electronic structure calculations provides insight into the reactivity of 1: JT-induced symmetry lowering provides an orbital selection mechanism for proton or H atom transfer reactivity.

Original languageEnglish (US)
Pages (from-to)12323-12336
Number of pages14
JournalJournal of the American Chemical Society
Issue number35
StatePublished - Sep 3 2014

ASJC Scopus subject areas

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


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