title: Catalytic NH3Synthesis using N2/H2at Molecular Transition Metal Complexes: Concepts for Lead Structure Determination using Computational Chemistry.
abstract: While industrial NH3synthesis based on the Haber-Bosch-process was invented more than a century ago, there is still no molecular catalyst available which reduces N2in the reaction system N2/H2to NH3. As the many efforts of experimentally working research groups to develop a molecular catalyst for NH3synthesis from N2/H2have led to a variety of stoichiometric reductions it seems justified to undertake the attempt of systematizing the various approaches of how the N2molecule might be reduced to NH3with H2at a transition metal complex. In this contribution therefore a variety of intuition-based concepts are presented with the intention to show how the problem can be approached. While no claim for completeness is made, these concepts intend to generate a working plan for future research. Beyond this, it is suggested that these concepts should be evaluated with regard to experimental feasibility by checking barrier heights of single reaction steps and also by computation of whole catalytic cycles employing density functional theory (DFT) calculations. This serves as a tool which extends the empirically driven search process and expands it by computed insights which can be used to rationalize the various challenges which must be met.
authors.affiliation: Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 2, 52074, Aachen, Germany.
authors.forename: Markus
authors.identifier: http://orcid.org/0000-0003-4088-8924
authors.initials: M
authors.lastname: Hölscher
authors.affiliation: Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 2, 52074, Aachen, Germany.
authors.forename: Walter
authors.identifier: http://orcid.org/0000-0001-6100-9656
authors.initials: W
authors.lastname: Leitner
keywords: NH3 synthesis; catalysis; density functional calculations; dinitrogen complexes; homogeneous catalysis