We have recently developed the coordination chemistry of new bis(thione) ligands such as the bis(mercaptoimidazolyl)methanes (BmmR) and bis(mercaptoimidazolyl)xylenes (BmxR).  All these air-stable sulfur-donor ligands are readily prepared and exhibit a rich coordination chemistry, examples of which include the synthesis of homoleptic copper(I) and silver(I) compounds [M(o-BmxR)2]+ (M = Cu, Ag; R = Me, But) and the isolation of indium(III) and bismuth(III) derivatives (o-BmxR)MX3 (M = In, Bi; X = Cl, Br).  We describe herein the preparation of the first three members of a new family of neutral tris(thione)ligands, the tris(mercaptoimidazolyl)mesitylenes R3TmmesMe (R = H, Me, Et).  The presence of the three methyl substituents in the benzene ring in Me3TmmesMe has an unexpected effect on its reactivity towards copper(I) ions.  Whereas TmmesMe reacts with copper(I) halides to form complexes of stoichiometry (TmmesMe)CuX (X = Cl, Br, I), the trimethylated ligand preferentially forms compounds of composition Cu2(Me3TmmesMe)X2.  A single-crystal x-ray diffraction study of the dichloro derivative reveals a complex three-dimensional structure that will be described in detail in this presentation together with ongoing reactivity studies using Et3TmmesMe.

Tris(mercaptoimidazolyl)mesitylenes (R<sub>3</sub>Tmmes<sup>Me</sup>): Synthesis, structures, and copper(I) coordination chemistry

239th National Meeting (2010)

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Tris(mercaptoimidazolyl)mesitylenes (R3TmmesMe): Synthesis, structures, and copper(I) coordination chemistry

Tris(mercaptoimidazolyl)mesitylenes (R₃Tmmes^Me): Synthesis, structures, and copper(I) coordination chemistry