Correlation of solid state and solution coordination numbers with infrared spectroscopy in five-, six-, and eight-coordinate transition metal complexes of DOTAM
文摘
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.