A synthetic procedure is described for the preparation of the tetradentate N2O2 ligands H2[H4]L1=6-(2-hydroxyphenyl)-2,5-diaza-3,3-dimethyl-1-(2-hydroxy-3-t-butyl-5-methyl- phenyl)heptane, H2[H2]L1 = 6-(2-hydroxyphenyl)-2,5-diaza-3,3-dimethyl-1-(2-hydroxy-3-t-butyl-5-methylphenyl)-1-heptene, and H2L1 = 6-(2-hydroxyphenyl)-2,5-diaza-3,3-dimethyl-1-(2- hydroxy-3-t-butyl-5-methylphenyl)-1,5-heptadiene, which are asymmetric derivatives of the ligands tetrahydrosalen, dihydrosalen, and salen. Complexes Ni[H4]L1, Ni[H2]L1, NiL1, CoL1, Ni[H4]L2 (([H4]L2)2- = anion of H2[H4]L2 = N,N'-bis(2-hydroxy-3-t-butyl-5-methylbenzyl)- trans-(S,S)-1,2-diaminocyclohexane), and NiL2 were prepared, characterized (VIS and IR absorption, magnetic moment) and subjected to spectrophotometric titration with pyridine, to determine the equilibrium constants for adduct formation. Single crystal X-ray structure analyses were carried out for Ni[H2]L1 (monoclinic, P21/n; a = 8.926(4), b = 29.324(7), c = 8.411(4) Å; β = 95.3(1)°; Z = 4), CoL1 (monoclinic, C2/c; a = 25.389(2), b = 18.139(2), c = 10.179(1) Å; β = 112.227(6); Z = 8), and Ni[H4]L2·acetone (tetragonal, P41212; a = 13.928(3), c = 33.698(5) Å; Z = 8). In all of the three complexes, the N2O2-metal coordination core is square-planar. The skeleton of the tetradentate ligand is more or less twisted. The planar cobalt(II) complex CoL1 is a low spin d7 system with μexp = 2.02 BM at 298 K, whereas the planar complexes NiL1, Ni[H2]L1 and Ni[H4]L2 are diamagnetic (μexp = 0.28-0.64 BM). The blue solvate Ni[H4]L1- 3EtOH · H2O is paramagnetic (μexp = 3.04 BM), which points to octahedral coordination. In aerated acetone solution, the tetrahydrosalen-type complex Ni[H4]L1 activates dioxygen and one C-N bond is oxidatively dehydrogenated. The VIS spectrum of the dihydrosalen-type complex formed is virtually identical with that of the aldimine complex Ni[H2]L1. In the presence of dioxygen, Co[H4]L1 and Co[H2]L1 are readily oxidized to CoL1 in acetone solution.
α-(Imino)pyridyldifluoroethyl Phosphonates: Novel Promising Building Blocks in Synthesis of Biorelevant Aminophosphonic Acids Derivatives
