Cyclopentadienyl-Ruthenium and -Osmium chemistry. Some reactions of substituted vinylidene complexes.

Bruce, Michael I.; Swincer, A. Geoffrey; Wallis, Robert C.

doi:10.1016/s0022-328x(00)88073-0

Cited by 70 publications

(40 citation statements)

References 10 publications

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“…Cationic (M=C=CHR ? vinylidene complexes were previously made by protonation of metal-alkynyl derivatives [4][5][6][7]. An early established method of preparation of metal vinylidene consisted also in the addition of an electrophilic group at the b-carbon of alkynyl-metal complexes [8][9][10].…”

Section: Ruthenium-catalyzed Synthesis Of Vinyl-carbamatesmentioning

confidence: 99%

Early Steps of Homogeneous Catalysis in Rennes: Carbon Dioxide Incorporation, Alkyne Activation and Ruthenium Catalysis

Dixneuf

2014

Catal Lett

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This review reports the first discoveries in homogeneous catalysis in Rennes. Ruthenium(II) catalysts are shown to promote the activation of terminal alkynes and the synthesis of vinylcarbamates on addition of CO 2 and amines. The ruthenium-vinylidene are the key catalytic species. Applications to the addition of carboxylic acids to alkynes have opened the access to various enolesters and dienylesters via controlled catalyzed Markovnikov or anti-Markonikov additions. The catalytic synthesis of a-methylene cyclic carbonates and oxazolidinones from propargylic alcohols and CO 2 is presented and shown to lead to allene derivatives via palladium catalysis. Cp*RuX(COD) catalyst promote the head to tail oxidative couplings of alkene with alkyne, and the synthesis of functional dienes via 1,4 addition of H-nucleophiles to the biscarbene-ruthenium intermediate arising from head to head couplings of alkynes, whereas Cp*RuL 2 ? catalysts favour activation of alkynes via vinylidene intermediate.

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Section: Ruthenium-catalyzed Synthesis Of Vinyl-carbamatesmentioning

confidence: 99%

Early Steps of Homogeneous Catalysis in Rennes: Carbon Dioxide Incorporation, Alkyne Activation and Ruthenium Catalysis

Dixneuf

2014

Catal Lett

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“…+ and benzaldehyde (L = CO) or benzoic acid (L = PPh 3 ); [144] other examples of the oxidation of vinylidenes to carbonyls under ambient conditions are also known. [136,[145][146][147] Therefore the intermediacy of vinylidenes cannot be excluded in the conversion of alkynyl radical cations into carbonyls.…”

Section: Whereas Reaction Of For Example [Ru{c=c(h)-ph}l(pph 3 )Cp]mentioning

confidence: 99%

Ligand Redox Non‐Innocence in Transition‐Metal σ‐Alkynyl and Related Complexes

Schauer

Low

2011

Eur J Inorg Chem

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Transition-metal σ-alkynyl complexes are valuable functional materials that have found application as sructural units in the assembly of polymetallic arrays and large molecular structures, reagents for the transfer, oligomerisation or functionalisation of alkynes, magnetic or optical materials and putative components for use in a future molecular-based electronics platform. Many σ-alkynyl complexes are redoxactive, undergoing facile oxidation (reduction) at moderate potentials to generate radical cations (anions) in which the

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“…2) were reportedly synthesized from [CpRu(PPh 3 ) 2 Cl] (1) [Eq. (2); Cp = cyclopentadienyl], [17][18][19][20][21] stimulated a search for how such complexes may function as reactive intermediates in a catalytic cycle. These complexes are remarkably stable towards nucleophiles, for example, complex 2 must be heated at reflux in methanol to obtain the addition product.…”

Section: Additions Via Vinylidene Complexesmentioning

confidence: 99%

Ruthenium‐Catalyzed Reactions—A Treasure Trove of Atom‐Economic Transformations

2005

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The demand for new chemicals spanning the fields of health care to materials science combined with the pressure to produce these substances in an environmentally benign fashion pose great challenges to the synthetic chemical community. The maximization of synthetic efficiency by the conversion of simple building blocks into complex targets remains a fundamental goal. In this context, ruthenium complexes catalyze a number of non-metathesis conversions and allow the rapid assembly of complex molecules with high selectivity and atom economy. These complexes often exhibit unusual reactivity. Careful consideration of the mechanistic underpinnings of the transformations can lead to the design of new reactions and the discovery of new reactivity.

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Cyclopentadienyl-Ruthenium and -Osmium chemistry. Some reactions of substituted vinylidene complexes.

Cited by 70 publications

References 10 publications

Early Steps of Homogeneous Catalysis in Rennes: Carbon Dioxide Incorporation, Alkyne Activation and Ruthenium Catalysis

Early Steps of Homogeneous Catalysis in Rennes: Carbon Dioxide Incorporation, Alkyne Activation and Ruthenium Catalysis

Ligand Redox Non‐Innocence in Transition‐Metal σ‐Alkynyl and Related Complexes

Ruthenium‐Catalyzed Reactions—A Treasure Trove of Atom‐Economic Transformations

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