A simple and effective synthetic route to homo- and heteroleptic rare-earth (Ln = Y, La and Nd) complexes with a tridentate Schiff base anion has been demonstrated using exchange reactions of rare-earth chlorides with in-situ-generated sodium (E)-2-{[(2-methoxyphenyl)imino]methyl}phenoxide in different molar ratios in absolute methanol. Five crystal structures have been determined and studied, namely tris(2-{[(2-methoxyphenyl)imino]methyl}phenolato-κ3
O
1,N,O
2)lanthanum, [La(C14H12NO2)3], (1), tris(2-{[(2-methoxyphenyl)imino]methyl}phenolato-κ3
O
1,N,O
2)neodymium tetrahydrofuran disolvate, [La(C14H12NO2)3]·2C4H8O, (2)·2THF, tris(2-{[(2-methoxyphenyl)imino]methyl}phenolato)-κ3
O
1,N,O
2;κ3
O
1,N,O
2;κ2
N,O
1-yttrium, [Y(C14H12NO2)3], (3), dichlorido-1κCl,2κCl-μ-methanolato-1:2κ2
O:O-methanol-2κO-(μ-2-{[(2-methoxyphenyl)imino]methyl}phenolato-1κ3
O
1,N,O
2:2κO
1)bis(2-{[(2-methoxyphenyl)imino]methyl}phenolato)-1κ3
O
1,N,O
2;2κ3
O
1,N,O
2-diyttrium–tetrahydrofuran–methanol (1/1/1), [Y2(C14H12NO2)3(CH3O)Cl2(CH4O)]·CH4O·C4H8O, (4)·MeOH·THF, and bis(μ-2-{[(2-methoxyphenyl)imino]methyl}phenolato-1κ3
O
1,N,O
2:2κO
1)bis(2-{[(2-methoxyphenyl)imino]methyl}phenolato-2κ3
O
1,N,O
2)sodiumyttrium chloroform disolvate, [NaY(C14H12NO2)4]·2CHCl3, (5)·2CHCl3. Structural peculiarities of homoleptic tris(iminophenoxide)s (1)–(3), binuclear tris(iminophenoxide) (4) and homoleptic ate tetrakis(iminophenoxide) (5) are discussed. The nonflat Schiff base ligand displays μ2-κ3
O
1,N,O
2:κO
1 bridging, and κ3
O
1,N,O
2 and κ2
N,O
1 terminal coordination modes, depending on steric congestion, which in turn depends on the ionic radii of the rare-earth metals and the number of coordinated ligands. It has been demonstrated that interligand dihedral angles of the phenoxide ligand are convenient for comparing steric hindrance in complexes. (4)·MeOH has a flat Y2O2 rhomboid core and exhibits both inter- and intramolecular MeO—H...Cl hydrogen bonding. Catalytic systems based on complexes (1)–(3) and (5) have demonstrated medium catalytic performance in acrylonitrile polymerization, providing polyacrylonitrile samples with narrow polydispersity.
Tuning coordination modes of pyridine/thioether Schiff base (NNS) ligands to mononuclear manganese carbonyls
