A highly reactive triruthenium cluster complex bearing an alkyne coordinated in the .mu.3-.eta.2-perpendicular mode

Rivomanana, Soa; Lavigne, Guy; Lugan, Noël; Bonnet, Jean Jacques

doi:10.1021/ic00022a005

Cited by 44 publications

(18 citation statements)

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“…Beside compound 1, only few 46e Ru 3 species were reported in the literature. [4][5][6][7][8][9] Compound 1 was obtained by the reaction of [Ru 3 (CO) 10 (μ-dppm)] with the secondary phosphane PtBu 2 H, whereas in the first step of the reaction the species [Ru 3 (CO) 9 (μ-dppm)(PtBu t 2 H)] could be detected and isolated (also shown for P(1-Ad) 2 H and PCy 2 H). [2] Currently we are interested to examine that reaction behavior of secondary phosphanes in the related system [Ru 3 (CO) 10 (μ-dppa)] [10,11] and N-substituted derivatives of dppa respectively.…”

Section: Introductionmentioning

confidence: 99%

Electron‐Deficient Triruthenium Clusters Containing Small Bite‐Angle PNP‐Ligands

Böttcher

Heinemann

2021

Zeitschrift anorg allge chemie

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The ketyl-induced reaction of [Ru 3 (CO) 12 ] with N,N-bis (diphenylphosphanyl)n-propylamine (dpppra) in THF resulted in the expected metal cluster [Ru 3 (CO) 10 (μ-dpppra)] (2) in high yield. Compound 2 reacted in refluxing heptane with PBu t 2 H affording a new derivative of the rare type of 46-valence electron clusters [Ru 3 (μ-CO)(CO) 4 (μ-dpppra)(μ 3 -H)(μ-H)(μ-PtBu 2 ) 2 ](3) in good yield. The related cluster [Ru 3 (μ-CO)(CO) 4 (μdppa)(μ 3 -H)(μ-H)(μ-PtBu 2 ) 2 ] (4) (dppa = bis(diphenylphosphanyl) amine) was obtained in a similar manner in comparable yields. Compounds 2, 3, and 4 were spectroscopically characterized and their molecular structures in the solid were confirmed by single-crystal X-ray analysis.

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Section: Introductionmentioning

confidence: 99%

Electron‐Deficient Triruthenium Clusters Containing Small Bite‐Angle PNP‐Ligands

Böttcher

Heinemann

2021

Zeitschrift anorg allge chemie

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“…This suggests that these compounds are isostructural with the symmetrical derivative 3 11 whose dppm phosphorus atoms are equivalent and whose structure is proposed here to contain a CO and a dppm ligands bridging the same edge which is also parallel to the µ 3 -η 2 -alkyne 14 (see Scheme), although the X-ray molecular structure of the closely related cluster [Ru 3 (µ 3 -η 2 -PhC 2 CCPh)(µ-dppm)(µ-CO)(CO) 7 ] has been reported to be slightly different 15 with the bridging CO bonded to a different metal edge. Contrary to the analogous clusters 3, 4 and 5 and other clusters of the series containing a dppm instead of two CO ligands,11,16 it was impossible to decarbonylate 2 to yield the unsaturated cluster [Ru 3 (µ 3 -η 2 -FcCCC 6 H 4 -4-NO 2 )(µ-dppm)(CO) 7 ] with the alkyne bonded in the perpendicular mode. Compound 2 was stable when heated in toluene, at 80 °C, for 4 h, but upon increasing the temperature it underwent decomposition.…”

Section: Resultsmentioning

confidence: 94%

Electronic interactions in [Ru3(mu3-R² CCC6H4-4-R¹)(mu -dppm)(mu-CO) (CO)7] (R¹ = NO2 and R² = Fc; R¹ = NO2, CN and R² = Ph)

Rosseto¹,

Torres²,

Stein³

et al. 2003

J. Braz. Chem. Soc.

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A coordenação de FcCCC 6 H 4 -4-NO 2 (1) a uma carbonila polinucleada (cluster) de rutênio resultou na formação de [Ru 3 (µ 3 -FcCCC 6 H 4 -4-NO 2 )(µ-dppm)(µ-CO)(CO) 7 ] (2). Os voltamogramas cíclicos destes compostos e dos clusters análogos [Ru 3 (µ 3 -η 2 -C 6 H 5 CCC 6 H 4 -4-R)(µ-dppm)(µ-CO)(CO) 7 ] (R= H, 3; CN, 4; NO 2 , 5) permitiram avaliar as comunicações eletrônicas entre os diferentes sítios de oxi-redução (grupos ferrocenil e -NO 2 e o fragmento Ru 3 ) e analisar as capacidades relativas doadora-receptora de cada um dos três centros de oxi-redução que compõem 2. Além disto, a inércia de 2, em comparação com os clusters 3-5, os quais sofrem fácil perda de CO, foi atribuída à interação entre o grupo ferrocenil e a base metálica.The co-ordination of FcCCC 6 H 4 -4-NO 2 (1) to a ruthenium carbonyl cluster to yield [Ru 3 (µ 3 -FcCCC 6 H 4 -4-NO 2 )(µ-dppm)(µ-CO)(CO) 7 ] (2) is reported. The cyclic voltammograms of these compounds and of the analogous clusters [Ru 3 (µ 3 -η 2 -C 6 H 5 CCC 6 H 4 -4-R)(µ-dppm)(µ-CO)(CO) 7 ] (R= H, 3; CN, 4; NO 2 , 5) allowed an evaluation of the electronic communications between the different redox sites (ferrocenyl and -NO 2 groups, and Ru 3 moiety) and an analysis of the relative electron donor-acceptor capabilities of each of the three redox centres that compose 2. Furthermore, the inertness of 2, compared with clusters 3-5 which loose CO readily was attributed to the interaction between the ferrocenyl group and the metallic frame.Keywords: ruthenium cluster, ferrocene, alkyne, cyclic voltammetry IntroductionStudies of electronic interactions in systems containing multiple redox-active centres are of fundamental importance in the development of molecular-based electronic devices.1 Alkynes can be an elegant option in the search of systems containing multi-redox sites, once they can serve as conjugated bridges between groups of different electronic densities.2 In addition, they are remarkably versatile in their co-ordinating abilities to different metals (σ or π-fashion), that can result in the generation of novel mono or polynuclear metal complexes with attractive properties.3 Compounds derived from ferrocene have been extensively investigated for materials science 4 due to their low cost, stability and interesting redox properties, and can be used in molecular ferromagnets, molecular sensors, electrochemical agents, liquid crystals and non-linear optical materials. 5The aim of this work was to combine the electronic properties of alkynes, the ferrocenyl fragment and carbonyl clusters to build a new supramolecular compound containing various redox sites. Co-ordination of the ferrocenylalkyne FcCCC 6 H 4 -4-NO 2 (1) to a ruthenium carbonyl cluster to produce [Ru 3 (µ 3 -FcCCC 6 H 4 -4-NO 2 )(µ-dppm)(µ-CO)(CO) 7 ] (2) was therefore investigated. In cluster 2, the ferrocenyl fragment can act as an electron donor in charge-transfer processes, 6 the -NO 2 group as an electron acceptor 7 and the ruthenium moiety as a reservoir of electrons, depending on the co-ordinated ligands...

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“…Intramolecular akyne/CO/alkyne coupling dppm according to the sequence shown in Scheme 6. [40] While the synthetic utility of the halide appeared obvious A modification of our strategy was thus required in order in light of the above reactions, we rapidly faced a new prob-to observe full transformations of organic substrates on the lem while attempting to achieve a full transformation of metal core (see section I.3). the "activated" alkyne directed toward the liberation of an oligomeric substrate.…”

Section: Facile Dehydration Of a Cluster-bound Alkynolmentioning

confidence: 99%

Effects of Halides and Related Ligands on Reactions of Carbonylruthenium Complexes (Ru0–RuII)

Lavigne¹

1999

Eur. J. Inorg. Chem.

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While the primary motivation of fundamental studies on carbonylhalotriruthenium complexes was to understand the promoter effect of halides on certain ruthenium‐based catalytic systems of industrial relevance, such complexes have gained significance in their own right due to their remarkable ability to provide low‐activation energy pathways for the coordination of organic substrates. Limitations inherent to the fragility of these prototypes led to the design and development of a related family of more sophisticated derivatives where an aminopyridyl group serves as an alternate hemilabile ancillary ligand. Studies of their reactivity have revealed the possibility of achieving a number of stoichiometric or moderately catalytic “cluster‐mediated” transformations of organic substrates under very mild conditions. Yet, the viability of these systems is still limited to a narrow low‐energy domain. By contrast, halotriruthenium derivatives are still seen to function as catalyst precursors under the actual conditions of certain catalytic reactions where they act as sources of ruthenium(II) halide complexes that become the active components of the system. The second part of the review focuses on novel aspects of their fascinating chemistry.

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A highly reactive triruthenium cluster complex bearing an alkyne coordinated in the .mu.3-.eta.2-perpendicular mode

Cited by 44 publications

References 3 publications

Electron‐Deficient Triruthenium Clusters Containing Small Bite‐Angle PNP‐Ligands

Electron‐Deficient Triruthenium Clusters Containing Small Bite‐Angle PNP‐Ligands

Electronic interactions in [Ru3(mu3-R² CCC6H4-4-R¹)(mu -dppm)(mu-CO) (CO)7] (R¹ = NO2 and R² = Fc; R¹ = NO2, CN and R² = Ph)

Effects of Halides and Related Ligands on Reactions of Carbonylruthenium Complexes (Ru0–RuII)

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