Metal clusters as ligands. Substitution of fe ions in Fe/Mo/S clusters by thiophilic CuI ions.
Metal clusters as ligands. Substitution of fe ions in Fe/Mo/S clusters by thiophilic CuI ions.
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金属簇作为配体。
DOI：
10.1021/ic051860p
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发表时间：
2006
影响因子：
4.6
通讯作者：
Coucouvanis,Dimitri
中科院分区：
文献类型：
--
作者：
Koutmos,Markos;Coucouvanis,Dimitri
The reactivity of Fe/S and Fe/Mo/S clusters, similar or analogous to those occurring in biological systems, with thiophilic metal ions has not been explored. In this Communication, we demonstrate that synthesis of heteropolynuclear clusters with different coordination geometries for different metals at different sites is possible by metal substitution or by metal addition reactions. The two clusters we report herein ([(Cl4-cat)2Mo2Cu5Fe4S9(PnPr3)7(SPnPr3)2]PF6and [(Cl4-cat)2Mo2Cu6Fe4S10(PnPr3)8]) contain Fe, Mo, and Cu, which display pseudotetrahedral, pseudooctahedral, and pseudotrigonal geometries, respectively. The synthesis of these clusters is achieved by the addition of appropriate amounts of [Cu(CH3CN)4]+to [(Cl4-cat)2Mo2Fe8(PnPr3)6]. The formation of the different products is temperature- and solvent-dependent. The CuIunits incorporated into the metal cluster framework, either bind to available lone pairs of the already bridging S ligands or displace the less thiophilic Fe atoms. Among the essential features of these new molecules are recognizable Fe/S fragments including an Fe6S9core in the first cluster and the pentlandite Fe4Cu4S6core in the second cluster.
