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

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• 作者：Maika K.C.T. Nagata¹ ; Paul S. Brauchle¹ ; Sen Wang² ; Sarah K. Briggs¹ ; Young Soo Hong¹ ; Daniel W. Laorenza¹ ; Andrea G. Lee ; T. David Westmoreland ; ^{westmoreland@wesleyan.edu" class="auth_mail" title="E-mail the corresponding author}
• 关键词：DOTAM ; X-ray structure ; Infrared spectroscopy ; Coordination complex ; Solution structure
• 刊名：Polyhedron
• 出版年：2016
• 出版时间：16 August 2016
• 年：2016
• 卷：114
• 期：Complete
• 页码：299-305
• 全文大小：802 K

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.