Electronic interactions in Ferrocene- and Ruthenocene-functionalized Tetraazamacrcocyclic Ligand complexes of FeII/III, CoII, NiII, CuII and ZnII

• Verfasst von: Comba, Peter [VerfasserIn]
• Verfasst von: Linti, Gerald W. [VerfasserIn]
• Titel: Electronic interactions in Ferrocene- and Ruthenocene-functionalized Tetraazamacrcocyclic Ligand complexes of FeII/III, CoII, NiII, CuII and ZnII
• Verf.angabe: Peter Comba, Gerald Linti, Kathrin Merz, Hans Pritzkow, and Franz Renz
• Jahr: 2005
• Umfang: 6 S.
• Fussnoten: Gesehen am 22.02.2018 ; Article was first published online on 2 December 2004
• Titel Quelle: Enthalten in: European journal of inorganic chemistry
• Ort Quelle: Weinheim : Wiley-VCH, 1998
• Jahr Quelle: 2005
• Band/Heft Quelle: (2005), 2, Seite 383-388
• ISSN Quelle: 1099-0682
• DOI: doi:10.1002/ejic.200400617
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: Ferrocene
• Sach-SW: Macrocyclic ligands
• Sach-SW: Ruthenocene
• Sach-SW: Transition metals
• K10plus-PPN: 1570101027

Abstract

The syntheses of ferrocene- and ruthenocene-functionalized tetraazamacrocyclic ligands and their corresponding transition metal complexes are described. Reaction of N,N′-bis(2-aminoethyl)-1,3-propanediamine (2,3,2-tet) with 1,1′-diformylferrocene and 1,1′-diformylruthenocene produces the ligands fcmac and rcmac in 81−85% yield. Examination of their CuII, NiII, CoII, ZnII and FeII/III complexes by IR, UV/Vis, EPR and Mössbauer spectroscopy as well as by electrochemical studies suggests electronic communication between the two metal centers of each complex. The molecular structure of [CuII(fcmac)(FBF3)]BF4, determined by X-ray structure analysis, is reported and shows that the distance between the two metals is 4.54 Å. Stability constants, determined by potentiometric titration, indicate that the copper(II) complexes are of similar stability as those with unfunctionalized tetraazamacrocyclic ligands (e.g. cyclam = 1,4,8,11-tetraazacyclotetradecane); stability constants of cobalt(II) complexes are about 2 log units smaller, those of nickel(II) and zinc(II) complexes are reduced by more than 10 log units. This selectivity is discussed on the basis of the structural studies.