Chalcogen-Centered Spirocyclic Mixed-Metal Carbonyl Complexes: Synthesis and Molecular Structures of (CO)<sub>8</sub>(μ-PCy<sub>2</sub>)Re<sub>2</sub>(μ<sub>4</sub>-E)Fe<sub>2</sub>(μ-ER)(CO)<sub>6</sub> and [(CO)<sub>8</sub>(μ-PCy<sub>2</sub>)Re<sub>2</sub>(μ<sub>4</sub>-E)Fe<sub>2</sub>(CO)<sub>6</sub>]<sub>2</sub>(μ<sub>4</sub>-E<sub>2</sub>) (E = S, Se, Te; R = Organic Residue)
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When NEt4[Re2(μ-PCy2)(CO)8] (1) was reacted with Fe2(μ-E2)(CO)6 (E = S, Se, Te) in THF, the salts NEt4[(CO)8(μ-PCy2)Re2(μ4-E)Fe2(μ-E)(CO)6] (E = S (2a), Se (2b), Te (2c)) were formed. Their spirocyclic anions were trapped with MeI, giving the spirocyclic complexes (CO)8(μ-PCy2)Re2(μ4-E)Fe2(μ-EMe)(CO)6 (E = S (3a), Se (3b), Te (3c)). Their molecular structures were confirmed by single-crystal X-ray analysis. The anions of 2a−c are sensitive to oxidation. On crystallization in the presence of oxygen the corresponding dichalcogenides [(CO)8(μ-PCy2)Re2(μ4-E)Fe2(CO)6]2(μ4-E2) (E = S (4a), Se (4b), Te (4c)) were obtained in good yield. Their molecular structures were confirmed by single-crystal X-ray analysis. 2a was also trapped with CF3COOH, giving (CO)8(μ-PCy2)Re2(μ-S4)Fe2(μ-SH)(CO)6 (5). The latter can be expanded by SH oxidative addition of its μ-SH function to Os3(CO)11(NCMe), giving the mixed-metal carbonyl complex (CO)8(μ-PCy2)Re2(μ4-S)Fe2(CO)6(μ3-S)Os3(μ-H)(CO)11 (6). The framework of 6 could be derived from X-ray diffraction data. However, these data were insufficient for complete solution of the molecular structure, but spectroscopic data and elemental analysis of 6 are in accordance with the proposed molecular structure.
