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

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Title: 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
Author: Illingsworth, Marvin; Wang, Wei; Hughes, Kenneth; Terschak, John; McCarney, Jonathan; Stapleton, Russell; Wagner, Shawn; Trotter, Kari; Courtney, Raymond; Giacofei, Russel; Jensen, Andrew; Moisa, Marc; Browning, Todd; Puchebner, Birgit; Theimer, Carla; Chen, Yang
Abstract: 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-hydroxybenzylidende-4-nitro-N,N'-phenylenediamine [H2(ndsp)] and a functional group derivative of di-2-hydroxybenzylidene-N,N'-phenylenediamine [H2(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 anaylses, 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.
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Date: 2004

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