A Terminal Iron Nitrilimine Complex: Accessing the Terminal Nitride through Diazo N−N Bond Cleavage

Aghazada S, Miehlich M, Messelberger J, Heinemann FW, Munz D, Meyer K (2019)

Publication Type: Journal article

Publication year: 2019

Journal

Angewandte Chemie International Edition Wiley

DOI: 10.1002/anie.201910428

Abstract

A novel method for the N−N bond cleavage of trimethylsilyl diazomethane is reported for the synthesis of terminal nitride complexes. The lithium salt of trimethylsilyl diazomethane was used to generate a rare terminal nitrilimine transition metal complex with partially occupied d-orbitals. This iron complex 2 was characterized by CHN combustion analysis, 1H and 13C NMR spectroscopic analysis, single-crystal X-ray crystallography, SQUID magnetometry, 57Fe Mössbauer spectroscopy, and computational analysis. The combined results suggest a high-spin d 6 (S=2) electronic configuration and an allenic structure of the nitrilimine ligand. Reduction of 2 results in release of the nitrilimine ligand and formation of the iron(I) complex 3, which was characterized by CHN combustion analysis, 1H NMR spectroscopic analysis, and single-crystal X-ray crystallography. Treatment of 2 with fluoride salts quantitatively yields the diamagnetic FeIV nitride complex 4, with concomitant formation of cyanide and trimethylsilyl fluoride through N−N bond cleavage.

Authors with CRIS profile

Sadig Aghazada Lehrstuhl für Anorganische und Allgemeine Chemie Matthias Miehlich Lehrstuhl für Anorganische und Allgemeine Chemie Julian Messelberger Lehrstuhl für Anorganische und Allgemeine Chemie Frank Wilhelm Heinemann Lehrstuhl für Anorganische und Allgemeine Chemie Dominik Munz Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

How to cite

APA:

Aghazada, S., Miehlich, M., Messelberger, J., Heinemann, F.W., Munz, D., & Meyer, K. (2019). A Terminal Iron Nitrilimine Complex: Accessing the Terminal Nitride through Diazo N−N Bond Cleavage. Angewandte Chemie International Edition. https://doi.org/10.1002/anie.201910428

MLA:

Aghazada, Sadig, et al. "A Terminal Iron Nitrilimine Complex: Accessing the Terminal Nitride through Diazo N−N Bond Cleavage." Angewandte Chemie International Edition (2019).

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