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Functionalization of N2 by Mid to Late Transition Metals via N–N Bond Cleavage

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Book cover Nitrogen Fixation

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 60))

Abstract

This review focuses on the recent efforts to functionalize dinitrogen via complete cleavage of the N≡N bond with particular emphasis on mid to late transition metal complexes. The relationships of electronic and structural parameters for the most common N2-bonding modes (end-on and side-on bridging) with N2-splitting reactivity are discussed. This analysis points towards electronic configurations with π10 (end-on) and π8δ2 (side-on) electrons within the M2N2-cores for full N–N bond cleavage into terminal and bridging nitride complexes, respectively. The full body of work on N2-splitting with group 6–8 metals is comprehensively presented. Ligand electronic and steric effects are discussed in detail for privileged platforms, such as low coordinate, electron rich complexes with π-donating ligands. Finally, several strategies for functionalization of the nitrides resulting from N2-splitting are presented that lead to N–C bond formation. The developed pseudo-catalytic cycles reported so far that combine N2-cleavage, nitride functionalization, and N-transfer provide guidelines for rational catalyst design.

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  1. Institute for Inorganic Chemistry, University of Goettingen, Tammannstrasse 4, 37077, Goettingen, Germany

    Isabel Klopsch, Ekaterina Yu Yuzik-Klimova & Sven Schneider

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    Yoshiaki Nishibayashi

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Klopsch, I., Yuzik-Klimova, E.Y., Schneider, S. (2017). Functionalization of N2 by Mid to Late Transition Metals via N–N Bond Cleavage. In: Nishibayashi, Y. (eds) Nitrogen Fixation. Topics in Organometallic Chemistry, vol 60. Springer, Cham. https://doi.org/10.1007/3418_2016_12

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