T. Tanase, Sadao Nitta, S. Yoshikawa
Mar 1, 1992
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0
Influential Citations
44
Citations
Journal
Inorganic Chemistry
Abstract
The nickel(II) complex of N,N-dimethylethylenediamine (N,N-Me{sub 2}en), (Ni(N,N-Me{sub 2}en){sub 3})(ClO{sub 4}){sub 2} (1), in aqueous ethanol spontaneously adsorbed and fixed CO{sub 2} in air to give a trinuclear nickel(II) complex, (Ni{sub 3}(N,N-Me{sub 2}en){sub 6}(CO{sub 3})(H{sub 2}O){sub 4})(ClO{sub 4}){sub 4} (2). The complex 2 crystallizes in the hexagonal system 6. The structure was solved by direct methods and refined by least-squares techniques to a final R value of 0.065 for 2,940 independent reflections with F{sub o} > 3{sigma}(F{sub o}). The absolute configuration was determined by the Bijvoet method. The complex cation is trinuclear, which is made up of three octahedral nickel(II) complexes, {Lambda}-cis-(0,0)-(Ni(N,N-Me{sub 2}en){sub 2}(CO{sub 3})) and {Lambda}- and {Delta}-cis-(0,0)-(Ni(N,N-Me{sub 2}en)(H{sub 2}O){sub 2}){sup 2+}, joined by a novel hydrogen bonding network around the coordinating carbonate ligand. This planar hydrogen bonding system might stabilize the bidentate carbonate, resulting in the spontaneous fixation of CO{sub 2} in air. When analogous diamines (N,N{prime}-dimethylethylenediamine, N,N-diethylethylenediamine, N-methylethylenediamine, N-ethylethylenediamine) were used instead of N,N-Me{sub 2}en, no fixation of CO{sub 2} was observed. The N-substituent of diamines is an important factor in determining the occurrence of CO{sub 2} uptake.