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Transition Metal Nitride Complexes in Small Molecule Activation and Catalysis
Transition metal nitride (TMN) complexes constitute a well-established class of coordination compounds.[1] However, in contrast to related oxo species their role as key intermediates in molecular catalysis is largely underdeveloped. In this contribution, the electronic structures and chemical bonding in TMNs will be discussed as a basis for small molecule activation and catalysis. Two case studies will be presented. This is on the one hand the utilization of subvalent nitride ligands in late, electron rich TMNs for N-atom transfer catalysis. The distinct metallonitrene character enables photochemical C–H amination and amidation catalysis (Figure 1a).[2] On the other hand, formation of particularly strong metal-nitrogen multiple bonding can be exploited for (photo/electro-)chemical dinitrogen fixation strategies via N2 splitting (Figure 1b).[3,4]
[1] J. Smith, Progr. Inorg. Chem. 2014, 58, 417.
[2] (a) J. Sun, J. Abbenseth, H. Verplancke, M. Diefenbach, B. de Bruin, D. Hunger, C. Würtele, J. van Slageren, M.C. Holthausen, S. Schneider, Nat. Chem. 2020, 12, 1054. (b) T. Schmidt-Räntsch, H. Verplancke, J. N. Lienert, S. Demeshko, M. Otte, G. P. Van Trieste III, K. A. Reid, J. H. Reibenspies, D. C. Powers, M. C. Holthausen, S. Schneider, Angew. Chem. Int. Ed. 2022, e202115626.
[3] S. Forrest, B. Schluschaß, E. Yuzik-Klimova, S. Schneider, Chem. Rev. 2021, 121, 6522.
[4] (a) 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. (b) F. Schendzielorz, M. Finger, J. Abbenseth, C. Würtele, V. Krewald, S. Schneider, Angew. Chem. Int. Ed. 2019, 58, 830. (c) B. Schluschaß, J.-H. Borter, S. Rupp, S. Demeshko, C. Herwig, C. Limberg, N. Maciulis, J. Schneider, C. Würtele, V. Krewald, D. Schwarzer, S. Schneider, JACS Au 2021, 1, 879. (c) L. Alig, K. A. Eisenlohr, Y. Zelenkova, S. Rosendahl, R. Herbst-Irmer, S. Demeshko, M. C. Holthausen, S. Schneider, Angew. Chem. Int. Ed. 2022, 61, e202113340.
Hosted by Professor Alan Goldman
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