Nitrogen makes up 78% of the Earth’s atmosphere. Ammonia derived from N2 and fossil H2 in the Haber-Bosch process represents the main source of nitrogen compounds used in fertilizers as well as a base chemical for the synthesis of value-added products. In order to access a more diverse range of N-containing chemicals without relying on NH3 as an intermediate, it is of high interest to develop tailored nitrogen-activating catalysts.

The complete splitting of the dinitrogen triple bond can be achieved thermally, photochemically, or electrochemically. While a few transition metal complexes are capable of photochemical dinitrogen activation, the mechanistic understanding of the underlying processes is still in its early stages. All known complexes for N2 photoactivation have a linear core of the form M-N-N-M which undergoes geometric and electronic changes during the light excitation process, however the nature of the responsible excited state is presently ill-defined.[1]

Here we will present our multi-tier approach to study the complex electronic structure of two types pf nitrogen photoactivation complex: The catalyst design based on pincer ligands of the Schneider group[2,3] and Sita’s series of homologous transition metal complexes[4-6]. We analyse the structures of two of Sita's molybdenum[4-6,7] and tungsten[4-6] complexes and their electronic spectra in terms of the molecular orbitals, difference densities and the charge-transfer numbers provided by the wavefunction analysis program TheoDORE[8,9]. We study in particular the charge transfer character of the individual excitations and find that the transitions of photochemically active complexes have more charge-transfer character and higher intensity.[10] While density functional theory (DFT) has proven to be a powerful tool for first insights into the differences between photochemically and thermally active N2-splitting complexes, in some cases the complexity of the electronic structure requires the use of multiconfigurational methods. For the rhenium complex of Schneider and coworkers we present a first multireference electronic structure analysis with a (16,16) active space based on density matrix renormalisation group (DMRG) that permits an appropriate treatment of spin-orbit coupling effects.

[1] V. Krewald, Dalton Trans. 2018, 47, 10320-10329, DOI: 10.1039/C8DT00418H.
[2] B. M. Lindley, R. S. van Alten, M. Finger, F. Schendzielorz, C. Würtele, A. J. M. Miller, I. Siewert, S. Schneider, J. Am. Chem. Soc. 2018, 140, 7922-7935, DOI: 0.1021/jacs.8b03755.
[3] F. Schendzielorz, M. Finger, J. Abbenseth, C. Würtele, V. Krewald, S. Schneider, Angew. Chem. Int. Ed. 2019, 58, 830-834, DOI:10.1002/anie.201812125.
[4] A. J. Keane, W. S. Farrell; B. L. Yonke; P. Y. Zavalij, L. R. Sita, Angew. Chem. Int. Ed. 2015, 54, 10220-10224, DOI: 10.1002/ange.201502293.
[5] P. P. Fontaine, B. L. Yonke, P. Y. Zavalij, L. R. Sita, J. Am. Chem. Soc. 2010, 132, 12273-12285, DOI: 10.1021/ja100469f.
[6] J. P. Reeds, B. L. Yonke, P. Y. Zavalij, L. R. Sita, J. Am. Chem. Soc. 2011, 133, 18602-18605, DOI: 10.1021/ja208669s.
[7] V. Krewald, Front. Chem. 2019, 7, 352, DOI: 10.3389/fchem.2019.00352.
[8] F. Plasser, H. Lischka, J. Chem. Theory Comput. 2012, 8, 2777, DOI: 10.1021/ct300307c.
[9] S. Mai, F. Plasser, J. Dorn, M. Fumanal, C. Daniel, L. González, Coord. Chem. Rev. 2018, 361, 74, DOI: 10.1016/j.ccr.2018.01.019.
[10] S. Rupp, F. Plasser, V. Krewald, Eur. J. Inorg. Chem. 2020, 1506-1518, DOI: 10.1002/ejic.201901304.