Activation of triruthenium carbonyl complexes by incorporation of hemilabile ancillary ligands containing alkoxo, amido, or thiolato groups. Generation of a reactive alkenyl complex

Lugan, Noël; Laurent, François; Lavigne, Guy; Newcomb, Timothy P.; Liimatta, Eric W.; Bonnet, Jean Jacques

doi:10.1021/om00039a046

Cited by 57 publications

(48 citation statements)

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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: 72%

“…In trinuclear rhenium clusters, [25] these ligands have hitherto behaved as m 3 -h 2 five-electron donor ligands. In the case of triruthenium [9±20] and triosmium clusters, [26] the m 3 -h 2 fiveelectron-donor coordination mode predominates (there are hundreds of examples) over the m-h 2 three-electron-donor coordination mode, for which only two examples, one for ruthenium [9] and one for osmium, [26] have been reported.…”

Section: Resultsmentioning

confidence: 99%

“…Data for 6: A semiempirical absorption correction was applied by using y scans, [37] with correction factors in the range 0.820 to 0.760. Non H-atoms (1) 13.835 (9) 11.672 (4) 11.283 (3) 13.124(1) b [] 9.471 (5) 15.927 (7) 11.96 (2) 17.642 (7) were refined anisotropically. All hydrogen atoms were isotropically refined.…”

Section: Methodsmentioning

confidence: 99%

“…The ruthenium derivatives [Ru 2 (m-NCPh 2 )(m-h 2 -CH 2 CCH 2 CCSiMe 3 )(CO) 6 ] [5] and [Ru 4 (m-h 2 -Me 2 pz)(m 4 -h 4 -MeCHCCCMe)(m-CO)(CO) 10 ] (Me 2 pz 3,5-dimethylpyrazolate) [6] arise from the insertion of diynes into a metal ± hydride bond of trinuclear cluster precursors. The osmium derivatives [Os 3 9 ] were recently obtained in the reaction of [Os 3 (m 3 -h 2 -FcCCCCFc)(CO) 10 ] [1a] with water. [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.…”

Section: Introductionmentioning

confidence: 99%

“…The osmium derivatives [Os 3 9 ] were recently obtained in the reaction of [Os 3 (m 3 -h 2 -FcCCCCFc)(CO) 10 ] [1a] with water. [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.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Resultsmentioning

confidence: 72%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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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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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2-Pyridone

Hulce

2001

Encyclopedia of Reagents for Organic Synthesis

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Activation of triruthenium carbonyl complexes by incorporation of hemilabile ancillary ligands containing alkoxo, amido, or thiolato groups. Generation of a reactive alkenyl complex

Cited by 57 publications

References 1 publication

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

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

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

2-Pyridone

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