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

Part of the Topics in Organometallic Chemistry book series (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.

Keywords

  • Bonding
  • Dinitrogen splitting
  • Nitrogen fixation
  • Transition metal nitrides

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  • DOI: 10.1007/3418_2016_12
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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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