Elsevier

Inorganic Chemistry Communications

Volume 61, November 2015, Pages 204-206
Inorganic Chemistry Communications

Short communication
Unsymmetrical cyrhetrenyl and ferrocenyl azines derived from 5-nitrofurane: Synthesis, structural characterization and electrochemistry

https://doi.org/10.1016/j.inoche.2015.10.007Get rights and content

Highlights

  • Unsymmetrical cyrhetrenyl and ferrocenyl azines derived from 5-nitrofurane were synthesized.

  • All complexes display a (E,E)-configuration in solution and solid state.

  • Electronic effects of the organometallic fragments correlate with the spectroscopic and electrochemical properties.

Abstract

A new series of unsymmetrical cyrhetrenyl and ferrocenyl azines that were monosubstituted [(η5-C5H4)–C(R)double bondN–Ndouble bondCH(5-NO2–2-C4H2O)]M {with Mdouble bondRe(CO)3 and Rdouble bondH (1a) or Rdouble bondMe (1b); Mdouble bondFe(η5-C5H5) and Rdouble bondH (2a) or Rdouble bondMe (2b)} and disubstituted [Fe{(η5-C5H4)–C(Me)double bondN–Ndouble bondCH(5-NO2–2-C4H2O)}2] (3a) were prepared by condensation reactions of the corresponding organometallic hydrazone [(η5-C5H4)–C(R)double bondN–NH2)]M with 5-nitro-2-furaldehyde. The 1H and 13C{1H} NMR spectra indicated that these compounds adopted an (E,E)-configuration about the ˃Cdouble bondN − bond and an s-trans conformation about the N1–N2 bond, and this result was confirmed by X-ray crystallographic analyses of 1a and 2b. The opposite electronic effects of the organometallic fragments correlate with the co-planarity of the [(η5-C5H4)–C(R)double bondN–Ndouble bondCH(5-NO2–2-C4H2O)] system, the reduction potential of the nitro group (E1/2) and the chemical shifts of the iminic carbons.

Graphical abstract

A new series of unsymmetrical cyrethrenyl and ferrocenyl azines monosubstituted and disubstituted derived from 5-nitrofurane have been prepared. They adopted an (E,E)-configuration in solution and in the solid stateas confirmed by X-ray structures of 1a and 2b.

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Section snippets

Acknowledgments

A.H.K. wishes to acknowledge FONDECYT-Chile (Projects 1150601 and 1110669) and D.I. Pontificia Universidad Católica de Valparaíso. J.G. wishes to acknowledge CONICYT and DEA for a Doctoral scholarship and D.I.-PUCV.

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