Assembly reaction systems containing a templete component [LM3]0,1- (M = Mo, W; L = fac-tridentate ligand), FeCl2, and Na2Q (Q = S, Se) afford variant cluster types depending upon L and M.  When L = 1,3,5-tert-butyl-1,3,5-triazacyclohexane, dinuclear, trinuclear, and cubane-type tetranuclear clusters are formed under different reaction stiochiometries. In the latter case, specific incorporation of Q atoms is possible leading to the previously unknown cluster cores [MFe3S3Q]3+/2+ isolated in a variety of clusters.  When L = tris(3,5-dimethylpyrazolyl)hydroborate, different reaction stoichiometries afford a broad family of cluster with cubane [WFe3S3Q]3+/2+, edge-bridged double cubane [W2Fe6S6Q2]2+, PN-type [W2Fe6S9-nQn]1+ (n = 0-3), and double-cuboidal [W2Fe4S9-nQn]2+/1+/0 (n = 0,3).  Structures are presented and reaction pathways are considered, including the use of selenide to demonstrate that template reactants provide MS3 components of assembled clusters.

New types of cluster assembly reactions involving MS<sub>3</sub> templates

243rd National Meeting (2012)

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New types of cluster assembly reactions involving MS3 templates

New types of cluster assembly reactions involving MS₃ templates