Poster Presentation 21st International Conference on Biological Inorganic Chemistry 2025

Exploring Reactivity of Mononuclear N-Polydentate Cu(II) Complexes with various oxidants (#406)

Anusree Mukherjee 1
  1. JSU, Jacksonville, ALABAMA, United States

Regioselective oxidation of hydrocarbons using a chemical catalyst that is cost-effective, robust and avoid self-oxidation is a challenge facing many synthetic chemists. 

Nature on the other hand, unequivocally performs such reactions under ambient conditions as many important biological transformations require activation of C-H bond. Copper containing metalloenzymes play a significant role in dioxygen activation and hydrocarbon functionalization in nature. The development of environmentally-friendly copper mediated oxidations with ecological oxidants has attracted considerable attention across many scientific disciplines. However, there is debate over which active oxygen species is responsible for chemical activity. 

Thorough spectroscopic characterization of synthetic analogues of copper oxidases has been essential for understanding the structure and function of the native enzyme and how to apply that knowledge towards rational catalyst design. We have synthesized copper containing coordination complexes supported by tetradentate ligands. We investigated the reactions of these Cu (II) complexes with hydrogen peroxide (H2O2), a strong oxidant toward different organic substrates. Furthermore, we will explore reactivity of these complexes with cumyl hydroperoxide to elucidate reaction mechanism. These experimental data will corroborate our theoretical findings. Our understanding of effects of ligand rigidity and denticity on the nature of peroxide bond cleavage products will be discussed.

  • Thomas M. Jones, Niharika Krishna Botcha, Sandugash Yergeshbayeva, Michael Shatruk, Anusree Mukherjee* “Investigating Reactivity and Electronic Structure of CuII-Polypyridyl Complexes and H2O2Inorganica Chimica Acta, 2021, 516, 120168
  • Nirupama Singh, Niharika K. Botcha, Mehmed Z. Ertem, Jens Niklas, Erik Farquahar, Oleg G. Poluektov, Anusree Mukherjee* “Reactivity of Bio-inspired Cu (II)(N2/Py2) Complexes with Peroxide at Room Temperature” Journal of Inorganic Biochemistry, 2019, 197, 110674 (https://doi.org/10.1016/j.jinorgbio.2019.03.014)
  • Bruce J. Pella, Jens Niklas, Oleg G. Poluektov, Anusree Mukherjee*, Effects of Denticity and Ligand Rigidity on Reactivity of Copper Complexes with Cumyl Hydroperoxide, Inorganica Chimica Acta, 2018, 483, 71 – 78