Carboncarbon coupling reactions on triruthenium clusters: synthesis and structure of Ru3(CO)9[μ3-η3-PhCCCC(H)Ph][μ2-NS(O)MePh] and Ru3(μ2-CO)(CO)7[μ3-η3-PhCCCC(H)Ph][μ3-NS(O)MePh]

Ferrand, Vincent; Gambs, Céline; Derrien, Nadine; Bolm, Carsten; Stœckli-Evans, Helen; Süß‐Fink, Georg

doi:10.1016/s0022-328x(97)00507-x

Cited by 20 publications

(13 citation statements)

References 48 publications

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“…Instead of an allyl ligand, the cluster now has a cyclooctenyl ligand spanning the same Ru−Ru edge as the hydrazido NH fragment. This ligand is attached to Ru(1) through C(21) and C(22) and to Ru(2) through C(22) in an analogous manner with that found previously for other triruthenium clusters having edge-bridging alkenyl ligands. ,– However, all these previous alkenyl clusters have been prepared from acyclic alkynes, and therefore they all have acyclic alkenyl ligands.…”

Section: Resultssupporting

confidence: 57%

Reactions of Conjugated Dienes with a Triruthenium Hydrido Carbonyl Cluster: Synthesis and Reactivity of Trinuclear Derivatives Having an Edge-Bridging Allyl Ligand

et al. 2008

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The reactions of the hydrido triruthenium complex [Ru 3 (µ-H)(µ 3 -κ 2 -HNNMe 2 )(CO) 9 ] (1; H 2 NNMe 2 ) 1,1-dimethylhydrazine) with conjugated dienes give trinuclear derivatives that contain edge-bridging allyl ligands. The isolated allyl products are [Ru 3 (µ-κ 3 -C 8 H 13 )(µ 3 -κ 2 -HNNMe 2 )(µ-CO) 2 (CO) 6 ] (2) from 1,3cyclooctadiene, [Ru 3 (µ-κ 3 -C 6 H 9 )(µ 3 -κ 2 -HNNMe 2 )(µ-CO) 2 (CO) 6 ] (4) from 1,3-cyclohexadiene, and [Ru 3 (µκ 3 -C 4 H 6 OMe)(µ 3 -κ 2 -HNNMe 2 )(µ-CO) 2 (CO) 6 ] (5) from cis-1-methoxybutadiene. While the cyclic structure of the allyl ligands of 2 and 4 forces these ligands to have an anti-anti arrangement, compound 5 contains an anti-MeO-syn-Me allyl ligand. This synthetic approach, which uses conjugated dienes as precursors to allyl ligands, represents an alternative to the use of alkynes having R-hydrogen atoms as precursors to allyl ligands, especially if the alkyne required to make a particular allyl ligand is unknown or difficult to obtain, as happens for cyclic alkynes. The cyclooctenyl derivative [Ru 3 (µ-κ 2 -C 8 H 13 )(µ 3 -κ 2 -HNNMe 2 )(µ-CO) 2 (CO) 6 ] (3) has also been obtained, as a minor product, from the reaction of 1 with 1,3-cyclooctadiene. A study of the reactivity of compound 2 has been performed. It undergoes protonation at the metal atoms to give the cationic derivative [Ru 3 (µ-H)(µ-κ 3 -C 8 H 13 )(µ 3 -κ 2 -HNNMe 2 )(µ-CO) 2 (CO) 6 ] + , which has an edge-bridging hydrido ligand and has been isolated as the [BF 4 ]salt (6). Hydride addition to compound 2 occurs at the allyl ligand to give uncoordinated cyclooctene. Treatment of 2 with tert-butylisocyanide leads to the CO-substitution derivative [Ru 3 (µ-κ 3 -C 8 H 13 )(µ 3 -κ 2 -HNNMe 2 )( t BuNC)(µ-CO) 2 (CO) 5 ] (7), whereas its reaction with diphenylacetylene affords 1,3-cyclooctadiene and the 1,2-diphenylethenyl derivative [Ru 3 (µ-κ 2 -PhCCHPh)(µ 3 -κ 2 -HNNMe 2 )(µ-CO) 2 (CO) 6 ] (8). Some of these results have been rationalized with the help of DFT calculations.

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Section: Resultssupporting

confidence: 57%

Reactions of Conjugated Dienes with a Triruthenium Hydrido Carbonyl Cluster: Synthesis and Reactivity of Trinuclear Derivatives Having an Edge-Bridging Allyl Ligand

et al. 2008

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“…[21] Early in our investigation, it appeared that both 2 and 3 resulted from one of the two possible insertion products mentioned in the introduction (Scheme 1, type A), in sharp contrast with what had been observed in the reaction of diphenylbutadiyne with a slightly different precursor, [Ru 3 (m-H)(m 3 -h 2 -pyNMe)(CO) 9 ], which led to the two isomers. [4] However, as shown below, indirect evidence for the existence (in one case) of the ªmissingº isomer (type B) was subsequently obtained.…”

Section: Resultsmentioning

confidence: 69%

“…[1b] Finally, an additional cluster complex bearing an ynenyl ligand attached to three metal atoms, namely [Ru 3 {m-NS(O)-MePh}(m 3 -h 3 -PhCHCCCPh)(CO) 9 ], was obtained through a metal-mediated acetylide ± vinylidene coupling. [21] All the above-mentioned data prompted us to study, in a collaborative project between our research groups, the reactivity of [Ru 3 (m-H)(m 3 -h 2 -ampy)(CO) 9 ] (1; Hampy 2-amino-6-methylpyridine) [11] with diynes. We used the ampy ligand because its methyl group facilitates the monitoring of the reactions by 1 H NMR spectroscopy, making it easier to see how many products are in the reaction mixtures.…”

Section: Introductionmentioning

confidence: 99%

Formation of Cyclopentadienyl and Ruthenacyclopentadienyl Derivatives through Ynenyl-Diyne and Ynenyl-Alkyne Couplings onto a Triruthenium Cluster Core

et al. 2001

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The compound [Ru3(mu-H)(mu3-eta2-ampy)(CO)9] (1; Hampy =2-amino-6-methylpyridine) reacts with diynes RC4R in THF at reflux temperature to give the ynenyl derivatives [Ru3(mu3-eta2-ampy)(mu-eta3-RC...CC-CHR)(mu-CO)2-(CO)6] (2: R=CH2OPh; 3: R=Ph). These products contain a 1,4-disubstituted butynen-3-yl ligand attached to two ruthenium atoms. The compound [Ru3(mu-eta2-ampy)[mu3-eta6-PhCC5(C...CPh)-HPh2](CO)7] (4), which contains an eta5-cyclopentadienyl ring and a bridging carbene fragment, has also been obtained from the reaction of 1 with diphenylbutadiyne. This compound arises from a remarkable [3+2] cycloaddition reaction of a preformed 1,4-diphenylbutynen-4-yl ligand with a triple bond of a second diphenylbutadiyne molecule. The reactivity of the ynenyl derivatives 2 and 3 with diynes and alkynes has been studied. In all cases, compounds of the general formula [Ru3(mu-eta2-ampy)[mu3-eta5-C(=CHR)C=CRCR1=CR2](CO)7] (5-17) have been obtained. They all contain a ruthenacyclopentadienyl fragment formed by coupling of the coordinated ynenyl ligand of 2 (R = CH2OPh) or 3 (R = Ph) with a triple bond of the new reagent (the CR1=CR2 fragment results from the incoming diyne or alkyne reagent). While most of the products derived from 2 have the alkenyl C=CHR fragment with a Z configuration (R cis to Ru), all the compounds obtained from 3 have this fragment with an E configuration. Except 2 and 3, all the cluster complexes described in this article have a five-electron donor ampy ligand attached to only two metal atoms, a coordination mode unprecedented in cluster chemistry.

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“…[13] The cluster complex [Ru 3 {µ- 9 ] also contains an ynenyl ligand, but in this case the ligand arises from an alkynylϪvinylidene coupling. [14] …”

Section: Synthesis Of Compounds 1 Andmentioning

confidence: 99%

Reactivity of a Triruthenium Ynenyl Cluster Complex with Diynes: Cluster-Mediated Combination of up to Three Substituted Butadiyne Molecules into a Carbon-Rich Hydrocarbyl Ligand

Cabeza

Rı́o

Moreno

et al. 2002

Eur. J. Inorg. Chem.

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The triruthenium ynenyl cluster complex [Ru 3 (µ 3 -η 2 -apyr)(µ-η 3 -MeCH=CCϵCMe)(µ-CO) 2 (CO) 6 ] (2; Hapyr = 2-aminopyrimidine) has been prepared in two steps from [Ru 3 (CO) 12 ], 2-aminopyrimidine and 2,4-hexadiyne. Its reactivity with two conjugated diynes has been studied. With 2,4-hexadiyne, it affords [Ru 3 (µ 3 -η 2 -apyr){µ-η 5 -MeCϵCC=CMeC(=CHMe)-CϵCMe}(µ-CO) 2 (CO) 5 ] (3), which contains a diynedienyl ligand that arises from the coupling of 2,4-hexadiyne with the hex-2-yn-4-en-4-yl ligand of 2, whereas the reaction of com-

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Carboncarbon coupling reactions on triruthenium clusters: synthesis and structure of Ru3(CO)9[μ3-η3-PhCCCC(H)Ph][μ2-NS(O)MePh] and Ru3(μ2-CO)(CO)7[μ3-η3-PhCCCC(H)Ph][μ3-NS(O)MePh]

Cited by 20 publications

References 48 publications

Reactions of Conjugated Dienes with a Triruthenium Hydrido Carbonyl Cluster: Synthesis and Reactivity of Trinuclear Derivatives Having an Edge-Bridging Allyl Ligand

Reactions of Conjugated Dienes with a Triruthenium Hydrido Carbonyl Cluster: Synthesis and Reactivity of Trinuclear Derivatives Having an Edge-Bridging Allyl Ligand

Formation of Cyclopentadienyl and Ruthenacyclopentadienyl Derivatives through Ynenyl-Diyne and Ynenyl-Alkyne Couplings onto a Triruthenium Cluster Core

Reactivity of a Triruthenium Ynenyl Cluster Complex with Diynes: Cluster-Mediated Combination of up to Three Substituted Butadiyne Molecules into a Carbon-Rich Hydrocarbyl Ligand

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