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Download fileMetal Clusters as Ligands. Substitution of Fe Ions in Fe/Mo/S Clusters by Thiophilic CuI Ions
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posted on 20.02.2006, 00:00 authored by Markos Koutmos, Dimitri CoucouvanisThe 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]PF6 and [(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 CuI units
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 Fe6S9
core in the first cluster and the pentlandite Fe4Cu4S6 core in the
second cluster.
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Thiophilic Cucoordination geometries2 Mo 2 Cu 5 Fe 4 S 92 Mo 2 Cu 6 Fe 4 S 102 Mo 2 Fe 8Fe Ionsmetal addition reactionsP n Pr 3metal cluster frameworkS ligandsmetal substitutionheteropolynuclear clustersPF 6SP n Pr 3metal ClustersFe 6 S 9 corepentlandite Fe 4 Cu 4 S 6 coreCNthiophilic Fe atomsthiophilic metal ionsdisplay pseudotetrahedralpseudotrigonal geometries