Ruthenium-Based Heterocyclic Carbene-Coordinated Olefin Metathesis Catalysts

Vougioukalakis, Georgios C.; Grubbs, Robert H.

doi:10.1021/cr9002424

Cited by 1,834 publications

(1,101 citation statements)

References 409 publications

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“…24 Other articles are available that discuss recent advances in olefin metathesis by Ru catalysts. 25 …”

Section: Discovery Of High Oxidation State Multiple Metal-carbon Bondsmentioning

confidence: 99%

Metathesis by Molybdenum and Tungsten Catalysts

Schrock¹

2015

Chimia

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IntroductionIn the early 1970's organometallic, organic, and polymer chemists were attracted to a new type of catalytic reaction called Olefin Disproportionation by Banks and Bailey, who published results in the open literature in 1964; 1 the reaction also was reported by Natta in 1964 2 and had appeared in patents filed at duPont 3 and Standard Oil 4 several years earlier. The basic process, which was shown to be catalyzed by various molybdenum or tungsten, and later rhenium, compounds of unknown type, resulted in an "exchange" of alkylidene (usually CHR, where R = H or alkyl) units in alkenes with one another, e.g., propylene could be equilibrated with ethylene and cis and trans-2-butenes (equation 1) or norbornene could be polymerized through a "ringopening" of its double bonds (equation 2). Although several mechanisms were proposed, the correct one appeared first in a publication by Hérrison and Chauvin in 1971, 5 namely the reversible reaction between a metal complex that contains a metal-carbon double bond (M=CHR) and a C=C bond to yield an intermediate that contains a metallacyclobutane (MC 3 ) ring. A related reaction that involves alkynes was discovered to be catalyzed by a heterogeneous catalyst in 1968 6 and a homogeneous catalyst in 1972. 7 This "alkyne disproportionation" reaction was proposed to consist of a reversible reaction between a M≡CR bond (R≠H) and a C≡C bond to give all possible alkynes via a metallacyclobutadiene intermediate. 8 Neither process resulted in any positional isomerization of the C=C or C≡C bonds. Although Fischer-type "low oxidation state" carbene 9 complexes were known at the time, and the synthesis of carbyne complexes soon followed, 10 they did not promote what came to be known as alkene metathesis 11 and alkyne metathesis, respectively, in the rapid manner often observed for what are now known as "classical" alkene and alkyne metathesis catalysts. However, experiments first published in 1976 showed that polymerization of cyclic olefins, metathesis of linear olefins, enyne metathesis, and polymerization of acetylenes could be initiated by certain Fischer-type carbene complexes, although new alkylidenes of the same type as the initiator were not observed. 12 Classical metathesis catalysts often are formed from metal oxides on silica or alumina 13 or in solution from a variety of metal complexes. An alkylating agent is often required, but simply exposing the supported metal oxide to alkenes or alkynes at high temperatures will generate the catalyst through some unknown mechanism of mechanisms.

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“…24 Other articles are available that discuss recent advances in olefin metathesis by Ru catalysts. 25 …”

Section: Discovery Of High Oxidation State Multiple Metal-carbon Bondsmentioning

confidence: 99%

Metathesis by Molybdenum and Tungsten Catalysts

Schrock¹

2015

Chimia

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“…Many of the catalysts prepared in the Grubbs laboratory are commercially available and show high tolerance to a number of functional groups, thereby making the reaction widely applicable 2. It is even more remarkable that after many years of improvement in catalyst design and efficiency, the “simple” first generation Grubbs catalyst ( G1 , Fig.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular polymerization of a ureidopyrimidinone‐based [2]catenane prepared via ring‐closing metathesis

Teunissen

Berrocal

Corbet

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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“…However, we know relatively little about reaction classes in which a different type of union is made. For example, the ring-closing metathesis (RCM) reaction of a,w-dienes 1, using commercial Grubbs second-generation pre-catalyst 2, [2] forms the product rings 3 with a pbond and proceeds via a sequence of organoruthenium intermediates (Scheme 1). The RCM reaction has become one of the most powerfully transformative reactions in synthetic organic chemistry and is widely used for the synthesis of structurally complex molecules in the laboratory, [3] and in some cases, for industrial syntheses.…”

Section: Introductionmentioning

confidence: 99%

“…(1)], [1] which can be separated into enthalpic and entropic contributions [Eq. (2)]. This parameter can be evaluated from the reactant and product energies alone: [9] EM…”

Section: Introductionmentioning

confidence: 99%

Why is RCM Favoured Over Dimerisation? Predicting and Estimating Thermodynamic Effective Molarities by Solution Experiments and Electronic Structure Calculations

Nelson

Ashworth

Hillier

et al. 2011

Chemistry A European J

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The thermodynamic effective molarities of a series of simple cycloalkenes, synthesised from α,ω‐dienes by reaction with Grubbs’ second generation precatalyst, have been evaluated. Effective molarities were measured from a series of small scale metathesis reactions and agreed well with empirical predictions derived from the number of rotors and the product ring strain. The use of electronic structure calculations (at the M06‐L/6‐311G** level of theory) was explored for predicting thermodynamic effective molarities in ring‐closing metathesis. However, it was found that it was necessary to apply a correction to DFT‐derived free energies to account for the entropic effects of solvation.

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Ruthenium-Based Heterocyclic Carbene-Coordinated Olefin Metathesis Catalysts

Cited by 1,834 publications

References 409 publications

Metathesis by Molybdenum and Tungsten Catalysts

Metathesis by Molybdenum and Tungsten Catalysts

Supramolecular polymerization of a ureidopyrimidinone‐based [2]catenane prepared via ring‐closing metathesis

Why is RCM Favoured Over Dimerisation? Predicting and Estimating Thermodynamic Effective Molarities by Solution Experiments and Electronic Structure Calculations

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