Zur Darstellung phosphido‐chalkogenido‐verbrückter Dirheniumkomplexe vom Typ Re2(μ‐PCy2)(μ‐ER)(CO)8 (E = S,Se, Te; R = org. Rest) |
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Authors: | Hans Egold Stefanie Klose Ulrich Flrke |
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Abstract: | Synthesis of Phosphido Chalcogenido Bridged Dirhenium Complexes of the Type Re2(μ‐PCy2)(μ‐ER)(CO)8 (E = S, Se, Te; R = org. Residue) The reaction of Re2(μ‐Br)(μ‐PCy2)(CO)8 with nucleophiles MER (M = Na, Li; E = S, Se, Te; R = org. residue) gives via substitution of the bromido bridge phosphido chalcogenido bridged dirhenium complexes of the general formula Re2(μ‐PCy2)(μ‐ER)(CO)8. The new compounds were characterized by IR, 1H and 13C NMR spectroscopic data and by elemental analyses. In addition the molecular structures for E = S, Se, Te and R = Ph as well as for E = S and R = H, n‐Bu, 2‐pyridyl have been established by single crystal X‐ray analysis. 13C NMR spectra of Re2(μ‐PCy2)(μ‐EPh)(CO)8 (E = S, Se, Te) prove that the sulfur and selenium compounds are at room temperature dynamic molecules due to inversion of the pyramidal chalcogenido bridge. The tellurium compound, however, is rigid on the time scale of 13C NMR spectroscopy. Eventually the reactivity of the SH function of the novel complex Re2(μ‐PCy2)(μ‐SH)(CO)8 was investigated by reaction with Re2(CO)8(MeCN)2. In toluene at 90 °C the novel spirocyclic complex Re2(μ‐PCy2)(CO)8(μ4‐S)Re2(μ‐H)(CO)8 was formed by SH oxidative addition. |
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Keywords: | Rhenium Metal carbonyl complexes Organochalcogenolato bridges Organophosphido bridges Spirocyclic complexes |
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