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Correlation of Solid State and Solution Coordination Numbers with Infrared Spectroscopy in Five-, Six-, and
Maika K C T Nagata1, Paul S Brauchle1, Sen Wang1
1Department of Chemistry, Wesleyan University, Hall-Atwater Laboratories, Middletown, CT 06459.
Abstract:
Three new DOTAM (1,4,7,10-tetrakis(acetamido)-1,4,7,10-tetraazacyclododecane) complexes have been synthesized and characterized by X-ray crystallography: [Co(DOTAM)]Cl2•3H2O, [Ni(DOTAM)]Cl2•4H2O, and [Cu(DOTAM)](ClO4)2•H2O. Solid state and solution IR spectroscopic features for a series of [M(DOTAM)]2+ complexes (M=Mn, Co, Cu, Ni, Ca, Zn) correlate with solid state and solution coordination numbers. [Co(DOTAM)]2+, [Ni(DOTAM)]2+, and [Zn(DOTAM)]2+ are demonstrated to be six-coordinate in both the solid state and in solution, while [Mn(DOTAM)]2+ and [Ca(DOTAM)]2+ are eight-coordinate in the solid state and remain so in solution. [Cu(DOTAM)]2+, which is five-coordinate by X-ray crystallography, is shown to increase its coordination number in solution to six-coordinate.
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