Aqua bridge cleavage and metal ion extrusion by thiocyanate anions in a dicopper complex

Reaction of the imidazolidinyl phenolate-based ligand, H₃L (2-(2′-hydroxyphenyl)-1,3-bis4-(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 Cu^II ion. Whereas in 1:2 molar ratio, partial extrusion of the Cu^II ions takes place to generate in situ Cu(NCS)₃(OH₂)]⁻ anions. These complex anions then quantitatively replace anions in 1·1.5H₂O via ‘anion metathesis’ and concurrently remove the aqua bridge by coordination of linear MeCN to one of the Cu^II 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 Cu^II (S = 1/2) ions in a dinuclear entity exhibit ferromagnetic interactions (J/k_B = +15.0 K and g = 2.22) to yield an S_T = 1 spin ground state in good agreement with the M versus H data below 8 K.