Homodimetallic iron(II) hydrazones: syntheses, spectroscopic, electrochemical, and theoretical investigations. X-Ray crystal structure of both syn- and anti- rotamers of [(η5-Cp)Fe(η6-C6H5)–NHNC(Me)–(η5-C5H4) Fe(η5-Cp)]+PF6−

Carolina Manzur; Mauricio Fuentealba; Lorena Millán; Francisco Gajardo; David Carrillo; Jose A. Mata; Sourisak Sinbandhit; Paul Hamon; Jean-René Hamon; Samia Kahlal; and Jean-Yves Saillard

doi:10.1039/B107631K

Homodimetallic iron(II) hydrazones: syntheses, spectroscopic, electrochemical, and theoretical investigations. X-Ray crystal structure of both syn- and anti- rotamers of [(η⁵-Cp)Fe(η⁶-C₆H₅)–NHNC(Me)–(η⁵-C₅H₄) Fe(η⁵-Cp)]⁺PF₆⁻

Carolina Manzur,*^a Mauricio Fuentealba,^a Lorena Millán,^a Francisco Gajardo,^a David Carrillo,*^a Jose A. Mata,^b Sourisak Sinbandhit,^c Paul Hamon,^d Jean-René Hamon,*^d Samia Kahlal^e and and Jean-Yves Saillard*^e

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* Corresponding authors

^a Laboratorio de Química Inorgánica, Universidad Católica de Valparaíso, Valparaíso, Chile

^b Departamento de Química Inorgánica y Orgánica, Universitat Jaume I, Castellón, Spain

^c Centre Régional de Mesures Physiques de l'Ouest, Université de Rennes 1, Campus de Beaulieu, Rennes cedex, France

^d Laboratoire Organométalliques et Catalyse: Chimie et Electrochimie Moléculaires, (CNRS UMR 6509), Institut de Chimie de Rennes, Université de Rennes 1, Campus de Beaulieu, Rennes cedex, France

^e Laboratoire de Chimie du Solide et Inorganique Moléculaire, (CNRS UMR 6511), Institut de Chimie de Rennes, Université de Rennes 1, Campus de Beaulieu, Rennes cedex, France

Abstract

Two homogeneous series of homodimetallic iron(II) hydrazone complexes of general formula [CpFe(η⁶-p-RC₆H₄)–NHN [double bond, length half m-dash] CH–(η⁵-C₅H₄)FeCp]⁺PF₆⁻ (Cp = η⁵-C₅H₅): R = H, [5]⁺PF₆⁻; Me, [6]⁺PF₆⁻; MeO, [7]⁺PF₆⁻; Cl, [8]⁺PF₆⁻; and [CpFe(η⁶-p-RC₆H₄)–NHNCMe–(η⁵-C₅H₄)FeCp]⁺PF₆⁻: R = H, [9]⁺PF₆⁻; Me, [10]⁺PF₆⁻; MeO, [11]⁺PF₆⁻, have been prepared. These hydrazones were stereoselectively obtained as their trans isomers about the N [double bond, length half m-dash] C double bond, by reaction of the corresponding organometallic hydrazines [CpFe(η⁶-p-RC₆H₄NHNH₂)]⁺PF₆⁻, R = H, [1]⁺PF₆⁻; Me, [2]⁺PF₆⁻; MeO, [3]⁺PF₆⁻; and Cl, [4]⁺PF₆⁻, with formylferrocene, CpFe(η⁵-C₅H₄–CHO), and acetylferrocene, CpFe(η⁵-C₅H₄–CO-Me), respectively. All the new compounds were characterized by elemental analysis and IR, UV-Vis and ¹H NMR spectroscopies. For compound [9]⁺PF₆⁻, the activation energy ΔG^# for the hindered rotations of the mixed sandwich [CpFe(η⁶-C₆H₅–)]⁺ (41.8 ± 0.9 and 41.2 ± 3.7 kJ mol⁻¹) and the ferrocenyl unit (40.0 ± 3.2 kJ mol⁻¹) about the –NH–N [double bond, length half m-dash] CMe– hydrazone backbone have been determined by variable temperature ¹H NMR spectroscopic studies. The electrochemical behavior of the dinuclear hydrazones was explored by cyclic voltammetry, and features the role of the cationic [CpFe(η⁶-arene)]⁺ moiety as an electron acceptor. The crystalline and molecular structure of [9]⁺PF₆⁻ was determined by single crystal X-ray crystallographic analysis. The structure shows the presence of both syn and anti rotamers in the asymmetric unit. The analysis of the electronic structure of [9]⁺ through DFT calculations indicate a strong perturbation of the metal centers by the hydrazone bridge as well as some metal-metal interaction through the bridge.

New Journal of Chemistry

Homodimetallic iron(II) hydrazones: syntheses, spectroscopic, electrochemical, and theoretical investigations. X-Ray crystal structure of both syn- and anti- rotamers of [(η⁵-Cp)Fe(η⁶-C₆H₅)–NHNC(Me)–(η⁵-C₅H₄) Fe(η⁵-Cp)]⁺PF₆⁻

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Homodimetallic iron(II) hydrazones: syntheses, spectroscopic, electrochemical, and theoretical investigations. X-Ray crystal structure of both syn- and anti- rotamers of [(η⁵-Cp)Fe(η⁶-C₆H₅)–NHNC(Me)–(η⁵-C₅H₄) Fe(η⁵-Cp)]⁺PF₆⁻

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