Well-characterized olefin metathesis catalysts that contain molybdenum

Murdzek, John S.; Schrock, Richard R.

doi:10.1021/om00149a048

Cited by 180 publications

(65 citation statements)

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“…The above synthetic routes to trialkoxymolybdenum(VI) alkylidynes represent a significant improvement compared to the original route to trialkoxyalkylidyne complexes, [16,33] which was more time-consuming and not amenable to large-scale production. However, the scope of these catalysts is yet to be fully studied, leaving questions about the strength and limitations of these catalytic species.…”

Section: Trialkoxymolybdenum(vi) Alkylidynes Prepared From Metallaazimentioning

confidence: 99%

Alkyne Metathesis: Catalysts and Synthetic Applications

2007

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There has been rapid progress and growing interest in alkyne metathesis within the past decade. The availability of highly active catalysts as well as their applications in both organic synthesis and polymer chemistry has served to motivate the advancement of this field. In this article, the development of several different metathesis catalysts, including two heterogeneous ones, are reviewed with an emphasis on comparing strengths and weaknesses. In Section 4, the applications of alkyne metathesis to synthesis of natural products, conjugated polymers as well as shape-persistent macrocycles are discussed. In the last section, a comparison of alkyne metathesis to the well established alkene metathesis is given. Developing an alkyne metathesis catalyst with both high reactivity and robustness to air and moisture remains an unsolved problem of this important and useful reaction.

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Section: Trialkoxymolybdenum(vi) Alkylidynes Prepared From Metallaazimentioning

confidence: 99%

Alkyne Metathesis: Catalysts and Synthetic Applications

2007

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“…Olefin metathesis has been discovered in the 1950's by researchers at Dupont, [1] but only in the past fifteen years has its applications in synthesis spurred widely, owing to the commercialization of durable catalysts prepared initially by Schrock [2] and Grubbs, [3] which culminated by the award of the Nobel prize in 2005. The first-generation Grubbs' catalyst, (PCy3)2Ru(Cl)2=C(H)(Ph), remains one of the most abundantly used homogeneous species for the metathesis reaction, although more durable and more active generations of catalysts have been produced since.…”

Section: Introductionmentioning

confidence: 99%

Substantiating the Influence of Pore Surface Functionalities on the Stability of Grubbs Catalyst in Mesoporous SBA‐15 Silica

Staub

Guillet‐Nicolas

Even

et al. 2011

Chemistry A European J

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The influence of pore surface functionalities in mesoporous SBA‐15 silica on the stability of a model olefin metathesis catalyst, namely Grubbs I, is substantiated. In particular, it is demonstrated that the nature of the interaction between the ruthenium complex and the surface is strongly depending on the presence of surface silanols. For this study, differently functionalized mesoporous SBA‐15 silica materials were synthesized according to standard procedures and, subsequently, the Grubbs I catalyst was incorporated into these different host materials. All of the materials were thoroughly characterized by elemental analyses, nitrogen physisorption at −196 °C, thermogravimetric analyses, solid‐state NMR spectroscopy, and infrared spectroscopy (ATR‐IR). By such in‐depth characterization of the materials, it became possible to achieve models for the surface/catalyst interactions as a function of surface functionalities in SBA‐15; for example, in the case of purely siliceous silanol‐rich SBA‐15, octenyl‐silane modified SBA‐15, and silylated equivalents. It was evidenced that large portions of the chemisorbed species that are detected spectroscopically arise from interactions between the tricyclohexylphosphine and the surface silanols. A catalytic study using diethyldiallylmalonate in presence of the various functionalized silicas shows that the presence of surface silanols significantly decreases the longevity of the ring‐closing metathesis catalyst, whereas the passivation of the surface by trimethylsilyl groups slows down the catalysis rate, but does not affect significantly the lifetime of the catalyst. This contribution thus provides new insights into the functionalization of SBA‐15 materials and the role of surface interactions for the grafting of organometallic complexes.

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“…These catalysts are divided in two main subclasses: 1) the d 0 early transition metal catalysts based on group 6 and 7 transition metals (Scheme 1a), [4][5][6][7][8][9] which are referred to as the Schrock-type complexes, and 2) the Ru complexes, i.e., the Grubbs-type complexes [10,11] as well as related systems [12][13][14][15] (Scheme 1b). Well-defined homogeneous catalysts present the advantage of working at rather low temperatures, giving good selectivities (not including stereoselectivity) and providing ways to implement structure-reactivity relationships, which are necessary for a rational development of the best catalytic system for a given reaction.…”

Section: Introductionmentioning

confidence: 99%

Strategies to Immobilize Well‐Defined Olefin Metathesis Catalysts: Supported Homogeneous Catalysis vs. Surface Organometallic Chemistry

Copéret,

Basset

2007

Adv Synth Catal

213

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This review is mainly devoted to a description of the strategies that have been implemented to develop well-defined olefin metathesis catalysts immobilized on solid supports. Two main approaches have been investigated involving supported homogenous catalysts or heterogeneous catalysts prepared by surface organometallic chemistry. Advantages, limitations and possible developments of these systems are discussed.

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Well-characterized olefin metathesis catalysts that contain molybdenum

Cited by 180 publications

References 1 publication

Alkyne Metathesis: Catalysts and Synthetic Applications

Alkyne Metathesis: Catalysts and Synthetic Applications

Substantiating the Influence of Pore Surface Functionalities on the Stability of Grubbs Catalyst in Mesoporous SBA‐15 Silica

Strategies to Immobilize Well‐Defined Olefin Metathesis Catalysts: Supported Homogeneous Catalysis vs. Surface Organometallic Chemistry

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