ABSTRACT: [Cu2(μ4-O)Cu2] and [Cu2(μ1,1-N3)4Cu2] geo- metrical arrangements are found in a new family of tetranuclear copper(II) complexes: [Cu4(μ4-O)(μ-cip)2Cl4](1), [Cu4(μ4-O)- (μ-cip)2(μ1,3-O2CPh)4] . 2CH3OH (2 .2CH3OH), and [Cu4(μ1,1-N3)4(μ-cip)2(N3)2] . DMF (3 . DMF) [Hcip = 2,6- bis(cyclohexyliminomethylene)-4-methylphenol; CH3OH = methanol; DMF = dimethylformamide]. These complexes have been characterized by X-ray crystallography, and their magnetic properties have been studied. 1 and 2 form quasi-tetrahedral [Cu4(μ4-O)] complexes, and 3 is the first example of a rhomboidal [Cu4(μ1,1-N3)] compound. Formation of the [Cu4] compounds is achieved via ligand-exchange reactions. The relative binding strength of the three ancillary ligands as N3- > PhCO2- >Cl- has been demonstrated from the core-conversion and peripheral ligand-exchange reactions. For the three complexes, the magnetic susceptibility measurements in the range of 1.8 300 K have been performed and modeled using two isolated S = 1/2 dimers based on the spin Hamiltonian H = 2J{SCu,1 .SCu,2} with J/kB = -513, -340, and -315 K for 1 3, respectively (where J is the exchange constant through the oxido phenoxido and azido phenoxido bridges, respectively).

New Phenoxido-Bridged Quasi-Tetrahedral and Rhomboidal [Cu4] Compounds Bearing μ4-Oxido or μ1,1-Azido Ligands: Synthesis, Chemical Reactivity, and Magnetic Studies

BERTOLASI, Valerio;
2011

Abstract

ABSTRACT: [Cu2(μ4-O)Cu2] and [Cu2(μ1,1-N3)4Cu2] geo- metrical arrangements are found in a new family of tetranuclear copper(II) complexes: [Cu4(μ4-O)(μ-cip)2Cl4](1), [Cu4(μ4-O)- (μ-cip)2(μ1,3-O2CPh)4] . 2CH3OH (2 .2CH3OH), and [Cu4(μ1,1-N3)4(μ-cip)2(N3)2] . DMF (3 . DMF) [Hcip = 2,6- bis(cyclohexyliminomethylene)-4-methylphenol; CH3OH = methanol; DMF = dimethylformamide]. These complexes have been characterized by X-ray crystallography, and their magnetic properties have been studied. 1 and 2 form quasi-tetrahedral [Cu4(μ4-O)] complexes, and 3 is the first example of a rhomboidal [Cu4(μ1,1-N3)] compound. Formation of the [Cu4] compounds is achieved via ligand-exchange reactions. The relative binding strength of the three ancillary ligands as N3- > PhCO2- >Cl- has been demonstrated from the core-conversion and peripheral ligand-exchange reactions. For the three complexes, the magnetic susceptibility measurements in the range of 1.8 300 K have been performed and modeled using two isolated S = 1/2 dimers based on the spin Hamiltonian H = 2J{SCu,1 .SCu,2} with J/kB = -513, -340, and -315 K for 1 3, respectively (where J is the exchange constant through the oxido phenoxido and azido phenoxido bridges, respectively).
2011
M., Sarkar; R., Clerac; C., Mathoniere; N. G. R., Hearns; Bertolasi, Valerio; D., Ray
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11392/1431333
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