Disubstituted vinylidene complexes of iron and ruthenium: nucleophilic properties of ν1-acetylide ligands

Abbott, Steven; Davies, Stephen G.; Warner, Peter

doi:10.1016/0022-328x(83)80211-3

Cited by 47 publications

(21 citation statements)

References 7 publications

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“…94,95 The S N 2-type displacement of alkyl halides by metal alkynyl complexes is among the most straightforward means to access disubstituted alkenylidene complexes. For example, ruthenium complex 71 gave rise to ruthenium alkynyl complex 72 on treatment with basic alumina, which slowly cyclized to metric reactions using more activated electrophiles (e.g., methyl iodide, ethyl iodide, 96 methyl triflate, 97 methyl fluorosulfonate, 98 and iodoacetonitrile 99 ).…”

Section: Metal Vinylidene Complexesmentioning

confidence: 99%

Transition Metal Vinylidene- and Allenylidene-Mediated Catalysis in Organic Synthesis

2019

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With their mechanistic novelty and various modalities of reactivity, transition metal unsaturated carbene (alkenylidene) complexes have emerged as versatile intermediates for new reaction discovery. In particular, the past decade has witnessed remarkable advances in the chemistry of metal vinylidenes and allenylidenes, leading to the evolution of a diverse array of new catalytic transformations that are mechanistically distinct from those developed in the previous two decades. This review aims to provide a survey of the recent achievements in the development of organic reactions that make use of transition metal alkenylidenes as catalytic intermediates and their applications to organic synthesis.

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Section: Metal Vinylidene Complexesmentioning

confidence: 99%

Transition Metal Vinylidene- and Allenylidene-Mediated Catalysis in Organic Synthesis

2019

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“…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]. The most straightforward method appeared to be the direct activation via 1,2-hydrogen migration of g 2 -coordinated terminal alkynes [11].…”

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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“…In seeking to develop more expeditious routes to cyanovinylidene complexes, it is worth noting that half-sandwich ruthenium acetylide complexes such as Ru(CCPh)(PPh 3 ) 2 Cp (1) react with a variety of electrophilic reagents [25,26] including H + [27], alkyl halides [28], trialkyloxonium salts [29], diazonium salts and carbon-based electrophiles [30], including the masked example B(C 6 F 5 ) 3 [31] halogens (Cl 2 , Br 2 , I 2 ) [32,33], and cyanogen bromide, which acts as a halogen transfer agent [34] also determined, and are briefly described here for completeness. DFT based computational studies on representative cyanovinylidene complexes have also been carried out, which together with the structural, electrochemical and spectroscopic data provide insight into the electronic structure of the cyanovinylidene ligand.…”

Section: Methodsmentioning

confidence: 99%

The synthesis, molecular and electronic structure of cyanovinylidene complexes

Long¹,

Brown²,

Man³

et al. 2012

Inorganica Chimica Acta

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Disubstituted vinylidene complexes of iron and ruthenium: nucleophilic properties of ν1-acetylide ligands

Cited by 47 publications

References 7 publications

Transition Metal Vinylidene- and Allenylidene-Mediated Catalysis in Organic Synthesis

Transition Metal Vinylidene- and Allenylidene-Mediated Catalysis in Organic Synthesis

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

The synthesis, molecular and electronic structure of cyanovinylidene complexes

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