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Aqua bridge cleavage and metal ion extrusion by thiocyanate anions in a dicopper complex
Authors:Supriti Paul,Corine Mathoniè  re,Rodolphe Clé  rac,Debashis Ray
Affiliation:a Department of Chemistry, Indian Institute of Technology, Kharagpur 721 302, India
b CNRS, UPR 8641, Centre de Recherche Paul Pascal (CRPP), Equipe “Matériaux Moléculaires Magnétiques”, 115 avenue du Dr. Albert Schweitzer, Pessac F-33600, France
c Université de Bordeaux, UPR 8641, Pessac F-33600, France
d CNRS, Université de Bordeaux, Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Groupe des Sciences Moléculaires, 87 avenue du Dr. Albert Schweitzer, Pessac F-33608, France
Abstract:Reaction of the imidazolidinyl phenolate-based ligand, H3L [(2-(2′-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine)] with Cu(ClO4)2·6H2O produces an aqua-bridged cationic reactant complex [Cu2(μ-H2O)(μ-L)][ClO4]·1.5H2O (1·1.5H2O). Solution phase interaction of 1·1.5H2O with SCN anions in 1:1 molar ratio leads to [Cu2(μ-L)(NCS)]·2H2O (2·2H2O) that does not possess anymore the reactive aqua bridge but instead a terminal SCN anion coordinated only to one CuII ion. Whereas in 1:2 molar ratio, partial extrusion of the CuII ions takes place to generate in situ [Cu(NCS)3(OH2)] anions. These complex anions then quantitatively replace View the MathML source anions in 1·1.5H2O via ‘anion metathesis’ and concurrently remove the aqua bridge by coordination of linear MeCN to one of the CuII ions to give [Cu2(μ-L)(CH3CN)][Cu(NCS)3(OH2)] (3). The literature unknown [Cu(NCS)3(OH2)] anion forms an intimate H-bonded assembly with the cationic part of 3 to yield a novel [Cu3] isosceles triangle. The precursor complex is known as antiferromagnetic whereas in 2·2H2O, the CuII (S = 1/2) ions in a dinuclear entity exhibit ferromagnetic interactions (J/kB = +15.0 K and g = 2.22) to yield an ST = 1 spin ground state in good agreement with the M versus H data below 8 K.
Keywords:N3O4 ligand   Dicopper   Aqua bridge   Thiocyanate coordination   Anion metathesis   Magnetic properties
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