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Synthesis and structural characterization of mixed-metal complexes of CuI with MOS3 cores (M = Mo, W) and of an unusual polymeric AgI/mercaptoimidazole complex with five different AgI coordination environments

Lookup NU author(s): Emeritus Professor Bill Clegg, Dr Luca Russo

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Abstract

Reaction of (NH4)(2)[MO2S2] (M = Mo or W) with KI, CuCl and 1,3-diazepane-2-thione (Diap) in acetone affords air-and moisture-stable mixed-metal cluster compounds [MOS3(CuDiap)(3)]I (1 and 2). Attempts to produce [WS4Ag2(Mim(Ph))(4)] (Mim(Ph) = 2-mercapto-1-phenylimidazole) led to the unexpected polymeric compound [Ag5I5(Mim(Ph))(4)](n) (4), subsequently obtained from a rational direct reaction between AgI and Mim(Ph) in chloroform. The complexes have been characterized by IR, H-1 and C-13 NMR spectroscopy, and single-crystal diffraction. 1 and 2 have crystallographic threefold rotation symmetry, with an incomplete distorted cube MS3Cu3 core bearing terminal oxo and Diap ligands on M and Cu, respectively. The cube vertex opposite M is empty, giving an overall +1 cationic cluster and a separate I- anion too distant from the three Cu atoms to be considered as covalently bonded and resulting in discrete ion pairs in the crystal structures. This arrangement is different from previously reported related OMS3(CuL)(3)X complexes (L = monodentate ligand, X = halide), in which X, when present, is directly bonded to one, two or three Cu atoms. 4 has a one-dimensional polymeric chain structure in which silver displays five different approximately tetrahedral coordination environments, iodide ions serve as mu(2), mu(3) and mu(4) bridges, and the thione ligands are each either terminal or bridging. This unusually complex structure for a relatively simple chemical formula represents only the fifth example of a complex (AgI)(n)L-m in which L is a neutral S-donor ligand, and the five structures display a wide range of individual features. In all three of the new structures, N-H center dot center dot center dot S and/or N-H center dot center dot center dot I hydrogen bonds are found.


Publication metadata

Author(s): Beheshti A, Clegg W, Khorramdin R, Nobakht V, Russo L

Publication type: Article

Publication status: Published

Journal: Dalton Transactions

Year: 2011

Volume: 40

Issue: 12

Pages: 2815-2821

Print publication date: 01/01/2011

ISSN (print): 1477-9226

ISSN (electronic): 1477-9234

Publisher: Royal Society of Chemistry

URL: http://dx.doi.org/10.1039/c0dt01195a

DOI: 10.1039/c0dt01195a


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