From Salicylaldehyde to Chiral Salen Sulfonates - Syntheses, Structures and Properties of New Transition Metal Complexes Derived from Sulfonato Salen Ligands

• Published in: European Journal of Inorganic Chemistry Vol. 2010; no. 28; pp. 4450 - 4461
• Main Authors: Delahaye, Émilie, Diop, Mayoro, Welter, Richard, Boero, Mauro, Massobrio, Carlo, Rabu, Pierre, Rogez, Guillaume
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.10.2010; WILEY‐VCH Verlag; Wiley
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chirality; Density functional calculations; Ferromagnetic coupling; Physical Sciences; Salen sulfonates; Science & Technology; Structure elucidation; SQUARE-PLANAR; CARBOXYLATE COORDINATION; OLEFIN EPOXIDATION; Density functional calculations; Ferromagnetic coupling; SOLID-STATE; OXYGEN; CIRCULAR-DICHROISM; Salen sulfonates; Chirality; ZEOLITE-Y; SCHIFF-BASE; MAGNETIC-PROPERTIES; CATALYTIC-ACTIVITY; Structure elucidation
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201000487

Coordination complexes derived from chiral and nonchiral sulfonato salen ligands {(SalenSO3)Na2: N,N′‐bis(5‐sulfonatosalicylidene)‐1,2‐diaminoethane disodium salt, [(R,R) and (S,S)‐CySalenSO3]NaK: (R,R) and (S,S)‐N,N′‐bis(5‐sulfonatosalicylidene)‐1,2‐diaminocyclohexane sodium–potassium salt} have been synthesized. The crystal structures of the chiral and nonchiral NiII complexes [Ni(SalenSO3)]Na2 (1) and [Ni((R,R)CySalenSO3)]NaK (2) were solved. The other chiral and nonchiral sulfonato salen complexes, [Cu(SalenSO3)]Na2 (4), [Cu((R,R)CySalenSO3)]NaK (5), [Cu((S,S)CySalenSO3)]NaK (6) and [Zn(SalenSO3)]Na2 (7) got hydrolyzed before suitable crystals could form. Yet, their hydrolysis led to the formation of single crystals of the residues of total or partial hydrolysis: 5‐sulfonatosalicylaldehyde sodium salt (A), N‐(5‐sulfonatosalicylidene)‐1,2‐diaminoethane copper(II) [Cu(SalSO3)] (8) and (R,R)‐N‐(5‐sulfonatosalicylidene)‐1,2‐diaminocyclohexane copper(II) {Cu[(R,R)CySalSO3]} (9). All compounds were studied with IR and UV/Vis spectroscopy; chiral compounds were also investigated by circular dichroism. The magnetic properties of the copper compounds were investigated. Whereas 8 shows intermolecular antiferromagnetic interactions between mononuclear CuII complexes, 7 presents a weak intramolecular ferromagnetic coupling (J = 0.66 cm–1, H = –JŜCu1ŜCu2), which has been rationalized by DFT calculations. Five new sulfonato salen chiral and nonchiral complexes have been synthesized and characterized. The crystal structures of the Ni complexes, as well as those of three other compounds resulting from the partial hydrolysis of the complexes, have been obtained; among the latter, there is a sulfonato‐bridged copper(II) dinuclear complex showing a small intramolecular ferromagnetic interaction.