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: email@example.com
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.
- (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.
- (a) A. R. McDonald, L. Que Jr, Coord. Chem. Rev. 2013, 257, 414–428.
- (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.
- B. Mondal, F. Neese, E. Bill, S. Ye (in revision, 2018).
All are cordially invited to attend.