Department of Chemistry
Indian Institute of Technology Delhi

Reactivity of High-Valent Iron Complexes: Electronic Structure Makes the Difference

Dr. Bhaskar Mondal
RWTH Aachen University, Aachen, Germany, Email:

Date: March 16th 2018 (Friday)
Time: 4:00 PM
Venue: Committee Room, Chemistry Department, 6th Floor

High-valent iron complexes are implicated in the catalytic cycle of several oxygenases and nitrogenase enzymes.1 This has been inspiring synthetic chemists over the past decades to develop complexes featuring enzyme-like functionalities.2 However, complicated electronic structures of such complexes hinder a clear understanding of their reactivity and thereby restrain further developments. Typically, multiconfigurational nature of the electronic ground state, ligand noninnocence, highly covalent metal-ligand bonding, and multi-state reactivity often challenge experimental as well as theoretical investigations. My current research employs sophisticated quantum chemical methods in combination with theoretical spectroscopy to decipher the electronic structure of high-valent iron complexes, which in turn guide a rational design of new species with improved reactivity. As representative examples, electronic structure contribution to the reactivity of oxo-iron(IV)3 and oxoiron(V)4 complexes will be discussed in the current lecture. The discussion will also shed light on how spectroscopic results from magnetic circular dichroism (MCD), electron paramagnetic resonance (EPR), and Mössbauer spectroscopy elegantly correlate with the electronic structure obtained from ab inito calculations based on complete active space selfconsistent field (CASSCF) methods.

  1. (a) J. Hohenberger, K. Ray, K. Meyer, Nat. Commun. 2012, 3, 720–13. (b) B. Mondal, L. Roy, F. Neese, S. Ye, Isr. J. Chem. 2016, 56, 763–772.
  2. (a) A. R. McDonald, L. Que Jr, Coord. Chem. Rev. 2013, 257, 414–428.
  3. (a) S. Ye, C. Kupper, S. Meyer, E. Andris, R. Navrátil, O. Krahe, B. Mondal, M. Atanasov, E. Bill, J. Roithová, et al., J. Am. Chem. Soc. 2016, 138, 14312–14325. (b) B. Mondal, C. Kupper, J. Serrano-Plana, I. Klawitter, F. Neese, M. Costas, S. Ye, F. Meyer, J. Am. Chem. Soc. 2017, 139, 8939–8949.
  4. B. Mondal, F. Neese, E. Bill, S. Ye (in revision, 2018).

All are cordially invited to attend.
Convener (Seminars)