ORGANOMETALLIC IRON(II) COMPLEXES CONTAINING P-SUBSTITUTED ACETOPHENONE-ARYLHYDRAZONE LIGANDS

A series of twelve new organometallic acetophenone-hydrazone complexes of general formula [(h 5-Cp)Fe(h 6-o-RC6H4)-NHN=CMe-C6H4-p-R]+PF6- (Cp= C5H5; R,R=H,Me, [5]+PF6-; H,MeO, [6]+PF6-; H,NMe2, [7]+PF6-; Me,Me, [8]+PF6-; Me,MeO, [9]+PF6-; Me,NMe2, [10]+PF6-; MeO,Me, [11]+PF6-; MeO,MeO, [12]+PF6-;...

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Autores principales:	Manzur,Carolina, Millán,Lorena, Figueroa,Walter, Hamon,Jean-René, Mata,Jose A., Carrillo,David
Lenguaje:	English
Publicado:	Sociedad Chilena de Química 2002
Materias:	Mixed sandwiches organometallic arylhydrazone acetophenome-arylhydrazone dipolar chomophores X-ray structure
Acceso en línea:	http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0366-16442002000400014
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spelling	oai:scielo:S0366-164420020004000142009-12-18ORGANOMETALLIC IRON(II) COMPLEXES CONTAINING P-SUBSTITUTED ACETOPHENONE-ARYLHYDRAZONE LIGANDSManzur,CarolinaMillán,LorenaFigueroa,WalterHamon,Jean-RenéMata,Jose A.Carrillo,David Mixed sandwiches organometallic arylhydrazone acetophenome-arylhydrazone dipolar chomophores X-ray structure A series of twelve new organometallic acetophenone-hydrazone complexes of general formula [(h 5-Cp)Fe(h 6-o-RC6H4)-NHN=CMe-C6H4-p-R]+PF6- (Cp= C5H5; R,R=H,Me, [5]+PF6-; H,MeO, [6]+PF6-; H,NMe2, [7]+PF6-; Me,Me, [8]+PF6-; Me,MeO, [9]+PF6-; Me,NMe2, [10]+PF6-; MeO,Me, [11]+PF6-; MeO,MeO, [12]+PF6-; MeO,NMe2, [13]+PF6-; Cl,Me, [14]+PF6-; Cl,MeO, [15]+PF6-; Cl,NMe2, [16]+PF6-) has been prepared by reaction between their corresponding organometallic hydrazine precursors [(h 5-Cp)Fe(h 6-o-RC6H4)-NHNH2]+PF6- (R=H, [1]+PF6-; Me, [2]+PF6-; MeO, [3]+PF6-; Cl, [4]+PF6-, and aromatic ketones of the type MeC(=O)C6H4-p-R (R=Me, MeO, NMe2) in refluxing ethanol containing concentrated acetic acid. These mononuclear hydrazones were stereoselectively obtained as their trans-isomers about the N=C double bond, and were characterized by elemental analysis or high resolution mass spectrometry, I.R., UV-Vis, and ¹H NMR spectroscopies and, in the case of complex [11]+PF6- (R,R'=MeO,Me), by single-crystal X-ray diffraction analysis. The more salient features of this structure are: (i) the concomitant lengthening of the Fe-Cipso and the shortening of the Cipso-N bond distances leading to a slight iminium-cyclohexadienyl character of the coordinated C6 ring, (ii) the intramolecular hydrogen bonding between the benzylic N-H group and the oxygen atom of the ortho-methoxo-substituent, with the N(1)···O(1) separation of ca. 2.627(4) Å, and (iii) the slight deviation of coplanarity between the coordinated and the free phenyl rings (dihedral angle=15.60(0.25)°). Finally, the cyclic voltammetry studies reveal an irreversible one-electron reduction step for compounds [5-7]+PF6-, and the redox potentials clearly indicate that the reduction occurs at the cationic electron acceptor mixed sandwich unit.info:eu-repo/semantics/openAccessSociedad Chilena de QuímicaBoletín de la Sociedad Chilena de Química v.47 n.4 20022002-12-01text/htmlhttp://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0366-16442002000400014en10.4067/S0366-16442002000400014
institution	Scielo Chile
collection	Scielo Chile
language	English
topic	Mixed sandwiches organometallic arylhydrazone acetophenome-arylhydrazone dipolar chomophores X-ray structure
spellingShingle	Mixed sandwiches organometallic arylhydrazone acetophenome-arylhydrazone dipolar chomophores X-ray structure Manzur,Carolina Millán,Lorena Figueroa,Walter Hamon,Jean-René Mata,Jose A. Carrillo,David ORGANOMETALLIC IRON(II) COMPLEXES CONTAINING P-SUBSTITUTED ACETOPHENONE-ARYLHYDRAZONE LIGANDS
description	A series of twelve new organometallic acetophenone-hydrazone complexes of general formula [(h 5-Cp)Fe(h 6-o-RC6H4)-NHN=CMe-C6H4-p-R]+PF6- (Cp= C5H5; R,R=H,Me, [5]+PF6-; H,MeO, [6]+PF6-; H,NMe2, [7]+PF6-; Me,Me, [8]+PF6-; Me,MeO, [9]+PF6-; Me,NMe2, [10]+PF6-; MeO,Me, [11]+PF6-; MeO,MeO, [12]+PF6-; MeO,NMe2, [13]+PF6-; Cl,Me, [14]+PF6-; Cl,MeO, [15]+PF6-; Cl,NMe2, [16]+PF6-) has been prepared by reaction between their corresponding organometallic hydrazine precursors [(h 5-Cp)Fe(h 6-o-RC6H4)-NHNH2]+PF6- (R=H, [1]+PF6-; Me, [2]+PF6-; MeO, [3]+PF6-; Cl, [4]+PF6-, and aromatic ketones of the type MeC(=O)C6H4-p-R (R=Me, MeO, NMe2) in refluxing ethanol containing concentrated acetic acid. These mononuclear hydrazones were stereoselectively obtained as their trans-isomers about the N=C double bond, and were characterized by elemental analysis or high resolution mass spectrometry, I.R., UV-Vis, and ¹H NMR spectroscopies and, in the case of complex [11]+PF6- (R,R'=MeO,Me), by single-crystal X-ray diffraction analysis. The more salient features of this structure are: (i) the concomitant lengthening of the Fe-Cipso and the shortening of the Cipso-N bond distances leading to a slight iminium-cyclohexadienyl character of the coordinated C6 ring, (ii) the intramolecular hydrogen bonding between the benzylic N-H group and the oxygen atom of the ortho-methoxo-substituent, with the N(1)···O(1) separation of ca. 2.627(4) Å, and (iii) the slight deviation of coplanarity between the coordinated and the free phenyl rings (dihedral angle=15.60(0.25)°). Finally, the cyclic voltammetry studies reveal an irreversible one-electron reduction step for compounds [5-7]+PF6-, and the redox potentials clearly indicate that the reduction occurs at the cationic electron acceptor mixed sandwich unit.
author	Manzur,Carolina Millán,Lorena Figueroa,Walter Hamon,Jean-René Mata,Jose A. Carrillo,David
author_facet	Manzur,Carolina Millán,Lorena Figueroa,Walter Hamon,Jean-René Mata,Jose A. Carrillo,David
author_sort	Manzur,Carolina
title	ORGANOMETALLIC IRON(II) COMPLEXES CONTAINING P-SUBSTITUTED ACETOPHENONE-ARYLHYDRAZONE LIGANDS
title_short	ORGANOMETALLIC IRON(II) COMPLEXES CONTAINING P-SUBSTITUTED ACETOPHENONE-ARYLHYDRAZONE LIGANDS
title_full	ORGANOMETALLIC IRON(II) COMPLEXES CONTAINING P-SUBSTITUTED ACETOPHENONE-ARYLHYDRAZONE LIGANDS
title_fullStr	ORGANOMETALLIC IRON(II) COMPLEXES CONTAINING P-SUBSTITUTED ACETOPHENONE-ARYLHYDRAZONE LIGANDS
title_full_unstemmed	ORGANOMETALLIC IRON(II) COMPLEXES CONTAINING P-SUBSTITUTED ACETOPHENONE-ARYLHYDRAZONE LIGANDS
title_sort	organometallic iron(ii) complexes containing p-substituted acetophenone-arylhydrazone ligands
publisher	Sociedad Chilena de Química
publishDate	2002
url	http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0366-16442002000400014
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_version_	1718438152707768320

ORGANOMETALLIC IRON(II) COMPLEXES CONTAINING P-SUBSTITUTED ACETOPHENONE-ARYLHYDRAZONE LIGANDS

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