RESUMO
In this study, 28-membered macrocyclic 1,5(1,5)-di(1,5-diaza-3,7-diphosphacyclooctana)-2,4,6,8(1,4)-tetrabenzenacyclooctaphane were synthesized by condensation of pyridinephosphine, paraformaldehyde, and primary diamines (bis(4-aminophenyl)methane or -sulfide. The first representatives of binuclear copper(I) complexes of P,N-containing cyclophanes with two 1,5-diaza-3,7-diphosphacyclooctane rings incorporated into a macrocyclic core and intracavity location of unusual, developed angle Cu2I moiety were obtained. The structure of one complex was established by X-ray diffraction analysis. The complexation led to a slight distortion of the cyclophane conformations.
RESUMO
In order to synthesize new iron (II) complexes of 1,5-diaza-3,7-diphosphacyclooctanes with a wider variety of the substituents on ligands heteroatoms (including functionalized ones, namely, pyridyl groups) and co-ligands, it was found that these ligands with relatively small phenyl, benzyl, and pyridin-2-yl substituents on phosphorus atoms in acetonitrile formed bis-P,P-chelate cis-complexes [L2Fe(CH3CN)2]2+ (BF4)2-, whereas P-mesityl-substituted ligand formed only monoligand P,P-complex [LFe(CH3CN)4]2+ (BF4)2-. 3,7-dibenzyl-1,5-di(1'-(R)-phenylethyl)-1,5-diaza-3,7-diphosphacyclooctane reacted with hexahydrate of iron (II) tetrafluoroborate in acetone to give an unusual bis-ligand cationic complex of the composition [L2Fe(BF4)]+ BF4-, where two fluorine atoms of the tetrafluoroborate unit occupied two pseudo-equatorial positions at roughly octahedral iron ion, according to X-ray diffraction data. 1,5-diaza-3,7-diphosphacyclooctanes replaced tetrahydrofurane and one of the carbonyl ligands of cyclopentadienyldicarbonyl(tetrahydrofuran)iron (II) tetrafluoroborate to form heteroligand complexes [CpFeL(CO)]+BF4-. The structural studies in the solid phase and in solutions showed that diazadiphosphacyclooctane ligands of all complexes adopted chair-boat conformations so that their nitrogen atoms were in close proximity to the central iron ion. The redox properties of the obtained complexes were performed by the cyclic voltammetry method.