Date of Graduation

Spring 2013

Degree

Master of Science in Chemistry

Department

Chemistry

Committee Chair

Nikolay Gerasimchuk

Keywords

Bis-cyanoximes, supramolecular chemistry, coordination polymers, metal complexes, transition metals

Subject Categories

Chemistry

Abstract

The first non-chelating phenyl bis-cyanoximes (H2(1,3-BCO) and its isomer H2(1,4-BCO)) were synthesized and characterized by FT-IR spectroscopy, 1H, 13C, 1H-1H COSY NMR spectroscopy, UV-visible spectroscopy and X-ray analysis. H2(1,3-BCO) adopts four primary configurations as was confirmed by NMR analysis. Both ligands undergo deprotonation and form planar anions which exhibit solvatochromism in a variety of protic and aprotic solvents. A variety of new complexes, a series of monovalent Ag, Tl, and bivalent Cu and Ni complexes was prepared and characterized. Tl(I) complexes display short Tl—Tl interatomic distances, one exhibits porous channels. Ag(I) complexes are highly light-sensitive. Attempts were made to synthesize metal complexes using metalloligands of the formula [M(Am)nX2] (M = Cu, Ni; Am = 1,2-diaminomethane, 2,2'-dipyridyl and 1,10-phenanthroline; n = 2,3; X = Cl-, Br-, NO3-) Three of four 3d-metal complexes were found to contain trapped solvent molecules in their crystal structures. One of the complexes synthesized, [Cu(En)2(1,3-BCO)], exhibited binding of the cyano group to the Cu atom and was found to possess open space in its crystal structure.

Copyright

© Scott Michael Curtis

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