Functional Derivatives of [4-Amino-N,N′-bis(2-hydroxybenzidene)-1,2-phenylenediaminato][N,N′-bis(2-hydroxybenzidene)-1,2-phenylenediaminato]zirconium(IV), Zr(adsp)(Rdsp), for Use as Pendent Groups

• Published in: Synthesis and reactivity in inorganic and metal-organic chemistry 2004-03, Vol.34 (3), p.593-609
• Main Authors: Illingsworth, Marvin L., Wang, Wei, Hughes, Kenneth A., Terschak, John A., McCarney, Jonathan P., Stapleton, Russell A., Wagner, Shawn R., Trotter, Kari J., Courtney, Raymond E., Giacofei, Russel A., Jensen, Andrew J., Moisa, Marc S., Browning, Todd A., Puchebner, Birgit E., Theimer, Carla A., Chen, Yang
• Format: Article
• Language: English
• Subjects: Complex; Functional group derivatives; Pendent polymer; Schiff base; Zirconium
• ISSN: 0094-5714; 1532-2440
• DOI: 10.1081/SIM-120030443

The objective of this research was to prepare a variety of functional group derivatives of the eight-coordinate complex [4-amino-N,N′-bis(2-hydroxybenzidene)-1,2-phenylenediaminato][N,N′-bis(2-hydroxybenzidene)-1,2-phenylenediaminato]zirconium(IV), Zr(adsp)(dsp), for use as pendent groups on polymers. The synthetic method involved reaction of the free ligands di-2-hydroxybenzylidene-4-nitro-N,N′-phenylenediamine [H 2 (ndsp)] and a functional group derivative of di-2-hydroxybenzylidene-N,N′-phenylenediamine [H 2 (Rdsp), R = methyl, 3-methoxy, 5-methoxy, cyano, pyridyl nitrogen, and 3-fluoro substituents] with zirconium tetra-n-butoxide in 1:1:1 mole ratio, followed by column separation on silica gel and hydrogenation of the nitro group to amino group using hydrogen gas over Pd/C catalyst. The order of the latter two steps was chosen to affect the best column separation. Elemental analyses, physical data, FT-IR, and NMR spectral data for six new Zr(adsp)(Rdsp) complexes are reported. Eleven new Zr(ndsp)(Rdsp) and related homoleptic complexes are also included to corroborate spectral assignments.