title: Ligand influence over the formation of dinuclear [2+2] versus trinuclear [3+3] Cu(I) Schiff base macrocyclic complexes.
abstract: The preparation and characterization of three new macrocyclic ligands with pendant arms based on the [2+2] condensation of isophthalaldehyde and the corresponding triamine substituted at the central N-atom is reported. None of these new macrocyclic ligands undergo any equilibrium reaction, based on imine hydrolysis to generate [1+1] macrocyclic formation or higher oligomeric compounds, such as [3+3], [4+4], etc., at least within the time scale of days. This indicates the stability of the newly generated imine bond. In sharp contrast, the reaction of the [2+2] macrocyclic Schiff bases with Cu(I) generates the corresponding dinuclear Cu(I) complexes [Cu(2)(L(1))](2+), 1(2+); [Cu(2)(L(2))(CH(3)CN)(2)](2+), 2(2+); and [Cu(2)(L(3))(CH(3)CN)(2)](2+), 3(2+), together with their trinuclear Cu(I) homologues [Cu(3)(L(4))](3+), 4(3+); [Cu(3)(L(5))(CH(3)CN)(3)](3+), 5(3+); and [Cu(3)(L(6))(CH(3)CN)(3)](3+), 6(3+), where the [2+2] ligand has undergone an expansion to the corresponding [3+3] Schiff base that is denoted as L(4), L(5), or L(6). The conditions under which the dinuclear and trinuclear complexes are formed were analyzed in terms of solvent dependence and synthetic pathways. The new complexes are characterized in solution by NMR, UV-vis, and MS spectroscopy and in the solid state by X-ray diffraction analysis and IR spectroscopy. For the particular case of the L(2) ligand, MS spectroscopy is also used to monitor the metal assisted transformation where the dinuclear complex 2(2+) is transformed into the trinuclear complex 5(3+). The Cu(I) complexes described here, in general, react slowly (within the time scale of days) with molecular oxygen, except for the ones containing the phenolic ligands 2(2+) and 5(3+) that react a bit faster.
authors: Departament de Química, Universitat de Girona, Campus de Montilivi, E-17071 Girona, Spain.
authors: Arnau
authors: A
authors: Arbuse
authors: Sukanta
authors: S
authors: Mandal
authors: Somnath
authors: S
authors: Maji
authors: Ma Angeles
authors: MA
authors: Martínez
authors: Xavier
authors: X
authors: Fontrodona
authors: Diana
authors: D
authors: Utz
authors: Frank W
authors: FW
authors: Heinemann
authors: Sandra
authors: S
authors: Kisslinger
authors: Siegfried
authors: S
authors: Schindler
authors: Xavier
authors: X
authors: Sala
authors: Antoni
authors: A
authors: Llobet
mesh_terms: D000447:Aldehydes / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D008024:Ligands; D047028:Macrocyclic Compounds / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D012545:Schiff Bases / Q000737:chemistry
chemical_list: D000447:Aldehydes; D008024:Ligands; D047028:Macrocyclic Compounds; D009942:Organometallic Compounds; D012545:Schiff Bases; D003300:Copper