Silylalkin‐ und Silylvinyliden‐verbrückte Heterometallcluster

Bantel, Harald; Powell, Annie K.; Vahrenkamp, Heinrich

doi:10.1002/cber.19901230403

Cited by 21 publications

(3 citation statements)

References 19 publications

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“…8 The JH and 13C NMR data for complexes 2a and 3a are consistent with the structure of type A determined for compound 3a in the crystal. i This is the difference between complex 1 and the related heteronuclear complex RuCo2(CO)9(I~3-Me3SiC2Me ) that undergoes isomerization into a thermodynamically more stable vinylidene complex RuCo2(CO)9{~-C=C(SiMe3)Me } already at room temperature.…”

supporting

confidence: 78%

Alkyne-vinylidene coupling in the reactions of the alkyne complex Os3(μ-CO)(CO)9(μ3-Me3C2Me) with Me3SiC≡CR (R=Me, Bun). The structure and stereodynamic behavior of clusters Os3(CO)9{μ3-C(SiMe3)=C(Me)C=C(SiMe3)=C(Me)C=C(SiMe3)R} containing an osmacyclobutene moietycontaining an osmacyclobutene moiety

et al. 1998

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Reactions of the alkyne cluster Os3(g-CO)(CO)9(Ix3-Me3SiC2Me) with alkynes MejSiC-~CR (R = Me, Bu n ) in refluxing hexane result in the formation of clusters Og3(CO)9{la3-C(SiMe3)=C(Me)C=C(SiMe3)R} (2a: R = Me; 3a: R = Bun). The dienediyl ligand in these complexes is formed by alkyne-vinylidene coupling, with vinylidene generated in the course of reaction from the alkyne molecule by the acetylene-vinylidene rearrangement involving a 1,2-shift of the Me3Si group. The structure of cluster 3a was determined by X-ray structural analysis. The dienediyl ligand is coordinated to three metal atoms of the cluster framework by two n-ethylene bonds with two osmium atoms and two o-bonds with the third osmium atom with the formation of the osmacyclobutene moiety. The I I-I and 13C N M R study of 13CO-enriched samples of clusters 2a and 3a revealed the stereochemical nonrigidity of these molecules due to the exchange of the hydrocarbon and carbonyl ligands. Me ,~,~====~ "SiM e3 M eaSi-,....~ "~M,Q, ~ ';:"RSince only terminal CO ligands are present in complex 2a (IR spectral data), the possibility for each Os atom to have the 18-electron shell can only be provided by structure A. However, such a uniform electron distribution is not always observed in trimetallic clusters. The structure of cluster 2a could be unambiguously determined by X-ray structural analysis. Unfortunately, we failed to obtain a single crystal of this compound suitable for an X-ray study. To overcome this difficulty, in this work we used the reaction of complex 1 with Me3SiC---CBu n to obtain the red complex Os3(CO)9{i.t 3-C(SiMe3)=C(Me)C=C(SiMe3)Bu n} (3a), which, according to X-ray analysis data, appeared to have structure A. We also report the results of investigation of the temperature dependence of the IH and 13C NMR spectra of clusters 2a and 3a.* Results and DiscussionThe reaction of alkyne complex 1 with trimethylsilylhexyne was carried out in refluxing hexane, i.e., under conditions analogous to those described earlier t for the synthesis of complex 2a (Scheme 1). Separation * Data reported in this work were published in part as the preliminary communication)

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supporting

confidence: 78%

Alkyne-vinylidene coupling in the reactions of the alkyne complex Os3(μ-CO)(CO)9(μ3-Me3C2Me) with Me3SiC≡CR (R=Me, Bun). The structure and stereodynamic behavior of clusters Os3(CO)9{μ3-C(SiMe3)=C(Me)C=C(SiMe3)=C(Me)C=C(SiMe3)R} containing an osmacyclobutene moietycontaining an osmacyclobutene moiety

et al. 1998

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“…The initial product, [RuCo 2 (CO) 9 (μ 3 -Me 3 SiCϵCMe)], formed in the reaction underwent subsequent desilylation to give [RuCo 2 (CO) 9 (μ 3 -HCϵCMe)]. [20] In contrast to the highly stereoselective reactions with the other unsymmetrical alkynes above, the reaction of 1 with phenylacetylene afforded three isomeric alkyne butterfly clusters as red crystalline products (Scheme 4). The major product, obtained in 28 % yield, was identified as [Cp*IrRu 3 (CO) 9 (PhCCH)] (2g 3) ; it has been characterised spectroscopically and analytically, as well as by a singlecrystal X-ray structure analysis.…”

Section: Resultsmentioning

confidence: 99%

Reaction of the Heteronuclear Cluster [Cp*IrRu₃(μ‐H)₂(CO)₁₀] with Alkynes: Stereoselective Binding

Srinivasan

Leong

2006

Eur J Inorg Chem

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The reaction of the heteronuclear cluster [Cp*IrRu3(μ‐H)2(CO)10] (1) with the symmetrical alkynes RCCR (R = Ph, Et) afforded the butterfly clusters [Cp*IrRu3(CO)9(RCCR)] (2) and the trinuclear clusters [Cp*IrRu2(CO)7(RCCR)] (3) and [Ru3(CO)8(C4R4)] (4). The clusters 2 and 3 have the alkyne aligned parallel to an Ru–Ir bond. The reaction of 1 with unsymmetrical alkynes also afforded stereoselective binding of the alkyne such that the bulkier substituent was pointing away from the Cp*Ir moiety; with PhCCH, however, all three stereoisomers were obtained. With the bis‐silylated alkynes (R = SiMe3, SiEt3), loss of one trialkylsilyl group occurred to give [Cp*IrRu3(CO)9(HCCR)] and [Ru3(CO)9(μ‐H)(CCR)] (5). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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“…zur Trockne wurde der Ruckstand uber eine Kieselgelsaule 0.0346 (9) .O. 123 ( -.0402 ( (7) 0.063( 3) 0 A241 (9) 0.044 (3 ) 0.3843~3) 0.075(3) 0.3786m a.a31 (6) …”

Section: Diskussionunclassified

Alkin⇄Vinyliden‐Umwandlungen auf Vierkernclustern

1990

Self Cite

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The expansion of vinylidene-bridged FeCoz and RuCoz clusters 1 a -d, 2d with (cyclopentadieny1)rhodium building blocks 3a, b mainly yields alkyne-bridged FeCozRh Fur die Komplexchemie terminaler Alkine gilt allgemein, dalj der Alkinligand leicht der Tautomerisierung zum Vinylidenliganden unterliegt I), Dies wurde mehrfach fur einkernige,) und zweikernige Komplexe3) gezeigt, und wir konnten an zahlreichen Dreikernclustern die Umwandlung des p,-Alkin-in den p,-Vinyliden-Liganden beobachten4). Mit der Tautomerisierung ist im Falle der Cluster auch eine Verschiebung der Reaktivitat der C,-Einheit vom terminalen Alkin-C-Atom" zur vinylidenischen CHR-Gruppe6) verbunden.Wir sind bemuht, diesen Spezialfall einer metallkontrollierten organischen Reaktivitatssteuerung auszunutzen und die Bedingungen fur die Bevorzugung der p,-Vinyliden-bzw. p3-Alkin-Form auszuloten. Beim Studium entsprechender Silylalkin-Silylvinyliden-Umlagerungen unter Silylgruppenwanderung') wurden wir dabei auf die Moglichkeit aufmerksam, daD in Vierkernclustern wieder die Alkin-Form gegenuber der Vinyliden-Form bevorzugt ist.Wir wandten uns daher noch einmal den vinylidenverbruckten Basis-Clustern 1 und 24) zu rnit der Absicht, sie zu Vierkernclustern zu expandieren und so weiteres Material zur Alkin-Vinyliden-Tautomerie zu gewinnen. Nach einigen Vorversuchen erwiesen sich dann die Rhodiumverbindungen 3 als gute Expansionsreagenzien, die den Einstieg in die hier beschriebenen Reaktionen und Produkte eroffneten. Cluster-ExpansionenDie drei Cluster l b -d lieljen sich mit 3a durch Erhitzen in Toluol in die Vierkerncluster 4 b -d uberfuhren. Die Ausbeuten waren maljig bis gering, die Produkte thermisch und oxidativ recht stabil. Mit der Cluster-Expansion ging regelma13ig eine Umlagerung des Vinyliden-zum Alkinliganden einher. Auf die gleiche Weise gingen l a und b rnit 3b in die Cluster 5a und b uber, und das exemplarisch untersuchte RuCo,-System 2d bildete mit 3 a analog den Vierkerncluster 6 d.

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Silylalkin‐ und Silylvinyliden‐verbrückte Heterometallcluster

Cited by 21 publications

References 19 publications

Reaction of the Heteronuclear Cluster [Cp*IrRu₃(μ‐H)₂(CO)₁₀] with Alkynes: Stereoselective Binding

Alkin⇄Vinyliden‐Umwandlungen auf Vierkernclustern

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Silylalkin‐ und Silylvinyliden‐verbrückte Heterometallcluster

Cited by 21 publications

References 19 publications

Reaction of the Heteronuclear Cluster [Cp*IrRu3(μ‐H)2(CO)10] with Alkynes: Stereoselective Binding

Alkin⇄Vinyliden‐Umwandlungen auf Vierkernclustern

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Reaction of the Heteronuclear Cluster [Cp*IrRu₃(μ‐H)₂(CO)₁₀] with Alkynes: Stereoselective Binding