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‐hydroxybenzylidene‐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 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.
Acknowledgments
Acknowledgment is made to the Donors of the Petroleum Research Fund, administered by the American Chemical Society, the National Aeronautics and Space Administration Joint Venture program (NASA JOVE), the Olin Corporation Charitable Trust, the Council on Undergraduate Research, and the National Science Foundation Research Experiences for Undergraduates program (NSF REU) for partial support of this research. Additional funding from the RIT College of Science and Department of Chemistry, and technical support from Astra Arcus, USA, are also gratefully acknowledged.