A photochemical activation scheme of inert dinitrogen by dinuclear Ru(II) and Fe(II) complexes

Chemistry : a European Journal
Markus ReiherBernd Artur Hess

Abstract

A general photochemical activation process of inert dinitrogen coordinated to two metal centers is presented on the basis of high-level DFT and ab initio calculations. The central feature of this activation process is the occupation of an antibonding pi* orbital upon electronic excitation from the singlet ground state S0 to the first excited singlet state S1. Populating the antibonding LUMO weakens the triple bond of dinitrogen. After a vertical excitation, the excited complex may structurally relax in the S1 state and approaches its minimum structure in the S1 state. This excited-state minimum structure features the dinitrogen bound in a diazenoid form, which exhibits a double bond and two lone pairs localized at the two nitrogen atoms, ready to be protonated. Reduction and de-excitation then yield the corresponding diazene complex; its generation represents the essential step in a nitrogen fixation and reduction protocol. The consecutive process of excitation, protonation, and reduction may be rearranged in any experimentally appropriate order. The protons needed for the reaction from dinitrogen to diazene can be provided by the ligand sphere of the complexes, which contains sulfur atoms acting as proton acceptors. These prot...Continue Reading

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Citations

Apr 23, 2016·Accounts of Chemical Research·Hiromasa TanakaKazunari Yoshizawa
Sep 20, 2006·Angewandte Chemie·Hans-Jörg Himmel, Markus Reiher
May 11, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Vera Krewald
Oct 9, 2019·Proceedings of the National Academy of Sciences of the United States of America·Caiyun GengHelmut Schwarz
Jun 12, 2010·Inorganic Chemistry·Leslie D FieldScott J Dalgarno
May 12, 2021·Chemical Reviews·Sebastian J K ForrestSven Schneider
Oct 14, 2011·The Journal of Physical Chemistry. a·Shinya FurukawaTsunehiro Tanaka

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