title: Planar-chiral metal complexes comprised of square-planar metal and achiral tetradentate ligands: design, optical resolution, and thermodynamics.
abstract: Planar-chiral palladium complexes {[[N,N'-[1,4-butanediylbis(oxy-7,1-naphthalenediyl)]bis(2-pyridinecarboxamidato)](2-)-κN(1),κN(1)',κN(2),κN(2)']palladium (PdL(4)) and [[2,2'-[1,4-butanediylbis[[(oxy-7,1-naphthalenediyl)imino]methyl]]dipyrrolato](2-)-κN(1),κN(1)',κN(2),κN(2)']palladium (PdL(5))} were synthesized from achiral tetradentate ligands N,N'-[1,4-butanediylbis(oxy-7,1-naphthalenediyl)]bis(2-pyridinecarboxamide) (H(2)L(4)) and N,N'-bis[(1H-pyrrol-2-yl)methylidene]-7,7'-(1,4-butanediyldioxy)bis(1-naphthalenamine) (H(2)L(5)) bearing two dissymmetric bidentate units at both ends and a Pd(II) ion, respectively. The palladium complexes were crystallized in the monoclinic space group P2(1)/n with the unit cell parameters a = 16.5464(6) Å, b = 11.3534(4) Å, c = 17.6697(7) Å, β = 115.5300(10)°, and Z = 4 for PdL(4) and a = 17.2271(8) Å, b = 10.1016(5) Å, c = 17.9361(9) Å, β = 105.6310(10)°, and Z = 4 for PdL(5). The planar-chiral structures of PdL(4) and PdL(5) were confirmed by single-crystal X-ray analyses, resulting in the fact that the crystals were racemic mixtures. The racemic mixtures were successfully resolved by using chiral high-performance liquid-chromatography techniques. Racemizations of the complexes were found to be drastically dependent on the arrangement of the charged or uncharged metal-binding N atoms of the ligands.
authors.affiliation: Department of Industrial Chemistry, Faculty of Engineering, Tokyo University of Science, 12-1 Ichigaya-funagawara, Shinjuku, Tokyo 162-0826, Japan.
authors.forename: Hidetoshi
authors.initials: H
authors.lastname: Goto
authors.forename: Teppei
authors.initials: T
authors.lastname: Hayakawa
authors.forename: Kanako
authors.initials: K
authors.lastname: Furutachi
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Sugimoto
authors.forename: Shohei
authors.initials: S
authors.lastname: Inoue