Structure, reactivity, and spectroscopy of nitrogenase-related synthetic and biological clusters

The reduction of dinitrogen (N 2 ) is essential for its incorporation into nucleic acids and amino acids, which are vital to life on earth. Nitrogenases convert atmospheric dinitrogen to two ammonia molecules (NH 3 ) under ambient conditions. The catalytic active sites of these enzymes (known as FeM...

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Published inChemical Society reviews Vol. 5; no. 15; pp. 8743 - 8761
Main Authors Wang, Chen-Hao, DeBeer, Serena
Format Journal Article
LanguageEnglish
Published London Royal Society of Chemistry 02.08.2021
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Summary:The reduction of dinitrogen (N 2 ) is essential for its incorporation into nucleic acids and amino acids, which are vital to life on earth. Nitrogenases convert atmospheric dinitrogen to two ammonia molecules (NH 3 ) under ambient conditions. The catalytic active sites of these enzymes (known as FeM-cofactor clusters, where M = Mo, V, Fe) are the sites of N 2 binding and activation and have been a source of great interest for chemists for decades. In this review, recent studies on nitrogenase-related synthetic molecular complexes and biological clusters are discussed, with a focus on their reactivity and spectroscopic characterization. The molecular models that are discussed span from simple mononuclear iron complexes to multinuclear iron complexes and heterometallic iron complexes. In addition, recent work on the extracted biological cofactors is discussed. An emphasis is placed on how these studies have contributed towards our understanding of the electronic structure and mechanism of nitrogenases. In this review, recent studies on nitrogenase-related synthetic molecular complexes and biological clusters are discussed, with a focus on their reactivity and spectroscopic characterization.
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Serena DeBeer is a Professor and Director at the Max Planck Institute for Chemical Energy Conversion in Mülheim an der Ruhr, Germany. She also holds an Adjunct Professor in the Department of Chemistry and Chemical Biology at Cornell University and an honorary professorship at Ruhr University in Bochum. She received her Ph.D. from Stanford University in 2002. She was a staff scientist at the Stanford Synchrotron Radiation Laboratory from 2002-2009, before moving to a faculty position at Cornell. Research in the DeBeer group focuses on the development and application of advanced X-ray spectroscopic tools for understanding mechanisms in biological, homogeneous and heterogeneous catalysis.
Chen-Hao Wang completed his B.Sc. in Chemistry (2012) at National Chung Hsing University, Taiwan and M.Sc. (2014) at National Taiwan University under the supervision of Prof. Ching-Wen Chiu. He earned his Ph.D. (2020) at Texas A&M University, College Station. During his doctoral studies, he carried out research on bimetallic Ru
lattice-confined chemistry with Prof. David C. Powers. He is currently an Alexander von Humboldt Fellow at the Max Planck Institute for Chemical Energy Conversion in Mülheim an der Ruhr, Germany with Prof. Serena DeBeer. His post-doctoral research focuses on X-ray spectroscopic methods to interrogate reactivity and electronic properties of the FeMo-cofactor-related systems.
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ISSN:0306-0012
1460-4744
DOI:10.1039/d1cs00381j