TY - JOUR
T1 - Donor/acceptor organotriiron(II) hydrazone chromophores
T2 - Structural, spectroscopic and electrochemical properties
AU - Manzur, Carolina
AU - Millán, Lorena
AU - Fuentealba, Mauricio
AU - Mata, Jose A.
AU - Carrillo, David
AU - Hamon, Jean René
N1 - Funding Information:
The authors gratefully acknowledge Fondo Nacional de Desarrollo Cientı́fico y Tecnológico, FONDECYT (Chile), Grant No. 1010318 (D.C., C.M.), the Programme International de Coopération Scientifique, CNRS-CONICYT No. 16771 (C.M., D.C., J.-R.H.), the Pontificia Universidad Católica de Valparaı́so, the Universitat Jaume I, and the Université de Rennes 1 for financial support.
PY - 2005/3/1
Y1 - 2005/3/1
N2 - Two new trinuclear organoiron(II) complexes, in which a trans-1,2-ferrocenyl-ferrocenylene ethene unit (electron-donors) is attached to an electron-deficient cationic mixed sandwich via a conjugated hydrazone bridge, giving complexes of the type (E)-[CpFe(η5-C5H 4)-CH=CH-(η5-C5H4) Fe(η5-C5H4)-CH=NNH-(η6-p- RC6H4)FeCp]+PF6-(Cp= η5-C5H5;R=Me,4+PF 6-;MeO,5+PF6-), have been prepared. The complexes were fully characterised by 1H NMR, IR, UV-Vis spectroscopy. Their electrochemical properties have been studied by means of cyclic voltammetry, showing an effective electronic coupling between the two ferrocenyl fragments. The X-ray crystal structure of compound 4 +PF6- shows that it adopts the sterically more hindered syn-conformation about the 1,1′-ferrocenediyl core, with a parallel disposition of the conjugated dinucleating ligands, therefore, favouring an efficient electron delocalization through the entire π-framework. At the same time, the (C5-ring)Fe moieties adopt an anti,anti-conformation with the iron atoms on the opposite faces of their respective bridging ligand.
AB - Two new trinuclear organoiron(II) complexes, in which a trans-1,2-ferrocenyl-ferrocenylene ethene unit (electron-donors) is attached to an electron-deficient cationic mixed sandwich via a conjugated hydrazone bridge, giving complexes of the type (E)-[CpFe(η5-C5H 4)-CH=CH-(η5-C5H4) Fe(η5-C5H4)-CH=NNH-(η6-p- RC6H4)FeCp]+PF6-(Cp= η5-C5H5;R=Me,4+PF 6-;MeO,5+PF6-), have been prepared. The complexes were fully characterised by 1H NMR, IR, UV-Vis spectroscopy. Their electrochemical properties have been studied by means of cyclic voltammetry, showing an effective electronic coupling between the two ferrocenyl fragments. The X-ray crystal structure of compound 4 +PF6- shows that it adopts the sterically more hindered syn-conformation about the 1,1′-ferrocenediyl core, with a parallel disposition of the conjugated dinucleating ligands, therefore, favouring an efficient electron delocalization through the entire π-framework. At the same time, the (C5-ring)Fe moieties adopt an anti,anti-conformation with the iron atoms on the opposite faces of their respective bridging ligand.
KW - Arenehydrazone-iron complex
KW - Cyclopentadienyl-iron complex
KW - Electrochemistry
KW - Push-pull complex
KW - Sandwich complex
KW - X-ray structure
UR - http://www.scopus.com/inward/record.url?scp=14244261471&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2004.11.033
DO - 10.1016/j.jorganchem.2004.11.033
M3 - Article
AN - SCOPUS:14244261471
SN - 0022-328X
VL - 690
SP - 1265
EP - 1272
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 5
ER -