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Overcoming Statistical Complexity: Selective Coordination of Three Different Metal Ions to a Ligand with Three
Shigehisa Akine1, Takashi Matsumoto2, Tatsuya Nabeshima3
1Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan. akine@se.kanazawa-u.ac.jp.
Abstract:
In general, it is difficult to selectively introduce different metal ions at specific positions of a cluster-like structure. This is mainly due to statistical problems as well as the reversibility of the formation of coordination bonds. To overcome this statistical problem, we used a carefully designed ligand, H6 L, which can accommodate three different kinds of metal ions in three types of coordination sites. The complex [LNiZn2La](3+), which contains three different metals, was quantitatively obtained by a stepwise procedure, but different products were obtained when the metal ions were added in a different order. However, equilibration studies indicated that this complex was almost solely formed among 54 (=3×3×3H2) possible products upon heating; the formation efficiency (ca. 100%) was significantly higher than the statistical probability (2.47%). Such carefully designed ligands should be useful for the synthesis multimetallic systems, which are of interest because of the interplay between the different metals.
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