Ferrocene-containing chelating ligands. 1. Solution study, synthesis, crystal structure, and electronic properties of bis[l brace]N,N[prime]-ethylenebis((ferrocenylmethyl)amine)[r brace]copper(II) nitrate

Journal Article · Wed Mar 31 00:00:00 EST 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00059a028· OSTI ID:6208433

Benito, A; Cano, J; Martinez-Manez, R; Soto, J; Paya, J ^[1]; Lloret, F; Julve, M; Faus, J; Marcos, M D ^[2]

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1. Universidad Politecnica de Valencia (Spain)
2. Universitat de Valencia (Spain)

The synthesis of the Schiff base N,N[prime]-ethylenebis((ferrocenylmethylidene)amine),([eta][sup 5]-C[sub 5]H[sub 5])Fe[([eta][sup 5]-C[sub 5]H[sub 4])CH[double bond]N(CH[sub 2])[sub 2]N[double bond]CH([eta][sup 5]-C[sub 5]H[sub 4])]Fe([eta][sup 5]-C[sub 5]H[sub 5]) (1), its parent amine ([eta][sup 5]-C[sub 5]H[sub 5])Fe[([eta][sup 5]-C[sub 5]H[sub 4])CH[sub 2]NH(CH[sub 2])[sub 2]NHCH[sub 2]([eta][sup 5]-C[sub 5]H[sub 4])]Fe([eta][sup 5]-C[sub 5]H[sub 5]),Fc[sub 2]L (2), and the complex [Cu(Fc[sub 2]L)[sub 2](NO[sub 3])[sub 2]][center dot]2CH[sub 3]OH (3) are reported. The protonation of 2 and its complex formation with copper(II) have been investigated by potentiometry in dimethyl sulfoxide (dmso)-water (80:20 w/w) mixtures at 25[degrees]C and 0.1 mol dm[sup [minus]3] KClO[sub 4]. The molecular structure of 3 has been determined by single-crystal X-ray analysis. Refinement of the atomic parameters by least-squares techniques gave a final R factor of 0.046 (R[sub w] = 0.051) for 2,941 unique reflections having I > 2.5[sigma](I). The structure of 3 consists of discrete [Cu(Fc[sub 2]L)[sub 2](NO[sub 3])[sub 2]] neutral units in which the copper(II) ion exhibits a distorted octahedral environment: the four equatorial positions are occupied by the nitrogen atoms of the bidentate ligand, Fc[sub 2]L, whereas the apical sites are filled by oxygen atoms of weakly coordinated nitrate anions. 3 is actually a pentanuclear complex with four ferrocene groups which oxidize at the same potential as shown by cyclic voltammetry. So, this compound is a four-electron reservoir potentially capable of acting as a multielectron mediator in redox catalytic reactions. Its electronic properties have been characterized by spectroscopic techniques and variable-temperature magnetic susceptibility measurements. 29 refs., 3 figs., 5 tabs.

• OSTI ID: 6208433
• Journal Information: Inorganic Chemistry; (United States), Vol. 32:7; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
COPPER COMPLEXES
CHEMICAL PREPARATION
MOLECULAR STRUCTURE
LIGANDS
ANIONS
CRYSTAL STRUCTURE
DMSO
ELECTROCATALYSTS
FERROCENE
LEAST SQUARE FIT
MAGNETIC SUSCEPTIBILITY
POTENTIOMETRY
TRICLINIC LATTICES
VOLTAMETRY
WATER
CATALYSTS
CHARGED PARTICLES
COMPLEXES
CRYSTAL LATTICES
DIENES
HYDROCARBONS
HYDROGEN COMPOUNDS
IONS
IRON COMPLEXES
MAGNETIC PROPERTIES
MAXIMUM-LIKELIHOOD FIT
NUMERICAL SOLUTION
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
POLYENES
SULFOXIDES
SYNTHESIS
TITRATION
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400400 - Electrochemistry