New Metal−Organic Polygons Involving MM Quadruple Bonds: M<sub>8</sub>(O<sub>2</sub>C<sup>t</sup>Bu)<sub>4</sub>(μ-SC<sub>4</sub>H<sub>2</sub>-3,4-{CO<sub>2</sub>}<sub>2</sub>)<sub>6</sub> (M = Mo, W)
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The reactions between M2(O2CtBu)4, where M = Mo or W, and thienyl-3,4-dicarboxylic acid (0.5−1.5 equiv) in toluene proceed via a series of detectable intermediates to the compounds M8(O2CtBu)4(μ-SC4H2-3,4-{CO2}2)6, which are isolated as air-sensitive yellow (M = Mo) or red (M = W) powders and show parent molecular ions in their mass spectra (MALDI). The structure of the molybdenum complex was determined by single-crystal X-ray crystallography and shown to contain an unusual M8 polygon involving four Mo2 quadruply bonded units linked via the agency of the six 3,4-thienylcarboxylate groups. The structure has crystallographically imposed S4 symmetry and may be described in terms of a highly distorted tetrahedron of Mo2 units or a bisphenoid in which two Mo2 units are linked by a thienyldicarboxylate such that intramolecular Mo2···O bonding is present, while the other thienylcarboxylate bridges merely serve to link these two [Mo2]···[Mo2] units together. The color of the compounds arises from intense M2 δ-to-thienyl π* transitions and, in THF, the complexes are redox-active and show four successive quasi-reversible oxidation waves. The [M8]+ radical cations, generated by one-electron oxidation with AgPF6, are shown to be valence-trapped (class II) by UV−vis−near-IR and electron paramagnetic resonance spectroscopy. These results are supported by the electronic structure calculations on model compounds M8(O2CH)4(μ-SC4H2-3,4-{CO}2)6 employing density functional theory that reveal only a small splitting of the M2 δ manifold via mixing with the 3,4-thienylcarboxylate π system.
