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Issue 9, 2011
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Dimerization of pentanuclear clusters [Fe3Q(AsMe)(CO)9] (Q = Se, Te) as a conversion pathway to novel cubane-like aggregates

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Abstract

The first examples of carbonyl heterocubane-type clusters, [Fe43-Q)23-AsMe)2(CO)12] (2, Q = Se (a), Te (b)), which simultaneously contain elements of group 15 and 16, were obtained by thermolysis of [Fe33-Q)(μ3-AsMe)(CO)9] (1) in acetonitrile. The clusters 2 possess a cubic Fe4Q2As2 core with alternating Fe and Q/As atoms. The coordination environment of the Fe atoms is close to octahedral, and those of Q or As atoms are tetrahedral, which determines the distorted cubic cluster core geometry. The second main products of thermolysis are the clusters [Fe63-Q)(μ4-Q)(μ4-AsMe)2(CO)12] (3a,b), whose core contains double the elemental composition of the initial cluster 1. In the case of the Se-containing cluster two other minor products [Fe44-Se)(μ4-SeAsMe)(CO)12] (4) and [Fe33-AsMe)2(CO)9] (5) are formed. Based on the structures and properties of the products, a reaction route for the conversion of 1 into 2 is proposed, which includes the associative formation of the clusters 3 as intermediates, unlike the dissociative pathways previously known for the transformations of similar clusters of the type [Fe3Q2(CO)9].

Graphical abstract: Dimerization of pentanuclear clusters [Fe3Q(AsMe)(CO)9] (Q = Se, Te) as a conversion pathway to novel cubane-like aggregates

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Publication details

The article was received on 15 Nov 2010, accepted on 04 Jan 2011 and first published on 24 Jan 2011


Article type: Paper
DOI: 10.1039/C0DT01587C
Citation: Dalton Trans., 2011,40, 2067-2074
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    Dimerization of pentanuclear clusters [Fe3Q(AsMe)(CO)9] (Q = Se, Te) as a conversion pathway to novel cubane-like aggregates

    N. A. Pushkarevsky, S. N. Konchenko, M. Zabel, M. Bodensteiner and M. Scheer, Dalton Trans., 2011, 40, 2067
    DOI: 10.1039/C0DT01587C

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