Inhaltsu È bersicht. Die Umsetzung von Re 2 (l-Br)(l-PCy 2 )-(CO) 8 mit den Nucleophilen MER (M = Na, Li; E = S, Se, Te; R = org. Rest) fu È hrt durch Substitution der Bromidobru È cke zur Bildung von phosphido-chalkogenido verbru È ckten Dirheniumkomplexen des Typs Re 2 (l-PCy 2 )(l-ER)-(CO) 8 . Die neuen Komplexe wurden durch IR-, 1 H und 13 C-NMR-Spektren sowie Elementaranalysen charakterisiert. Fu È r E = S, Se, Te und R = Ph sowie fu È r E = S und R = H, n-Bu, 2-pyridyl gelang zudem die Charakterisierung mittels Einkristall-Ro È ntgenstrukturanalysen. Anhand der 13 C-NMR Spektren der Komplexe der Reihe Re 2 (l-PCy 2 )-(l-EPh)(CO) 8 (E = S, Se, Te) konnte gezeigt werden, daû die Komplexe mit E = S, Se bei Raumtemperatur einem fluxionalen Verhalten aufgrund einer permanenten Inversion am Schwefelatom bzw. Selenatom unterliegen. Die Tellurverbindung war dagegen als rigide auf der Zeitskala der 13 C-NMR-Spektroskopie anzusehen. Schlieûlich wurde die Reaktivita È t der SH-Funktion des neuen KomplexesAbstract. The reaction of Re 2 (l-Br)(l-PCy 2 )(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 Re 2 (l-PCy 2 )(l-ER)(CO) 8 . The new compounds were characterized by IR, 1 H and 13 C 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. 13 C NMR spectra of Re 2 (l-PCy 2 )(l-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 13 C NMR spectroscopy. Eventually the reactivity of the SH function of the novel complex Re 2 (l-PCy 2 )(l-SH)(CO) 8 was investigated by reaction with Re 2 (CO) 8 (MeCN) 2 . In toluene at 90°C the novel spirocyclic complex Re 2 (l-PCy 2 )-(CO) 8 (l 4 -S)Re 2 (l-H)(CO) 8 was formed by SH oxidative addition.
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.
The title compound, [Re2{μ‐S2NC(Et2)}(μ‐PCy2)(CO)8] or [Re2(C5H10NS2)(C12H22P)(CO)8], is the first structurally characterized rhenium complex with a bridging dithiocarbamate ligand. The Re⋯Re distance is non‐bonding.
In the title compound, [PtRe4(C12H22P)2(CO)18] or [(mu-PCy2)(CO)8Re2]2Pt(CO)2 (Cy is cyclohexyl), two phosphido-bridged dirhenium groups are linked by a Pt(CO)2 unit and show different bonding patterns for stereochemical reasons. The Re--Re distances are 3.2620 (15) and 3.0739 (15) A, and the Pt--Re distances are 2.9165 (12), 2.9025 (15) and 2.8548 (13) A.
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