The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2018

Herndon, James W.

doi:10.1016/j.ccr.2019.213051

Cited by 10 publications

(8 citation statements)

References 1,313 publications

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“…1 Multiple bonds between carbon and transition metals have been studied extensively, and many such systems play integral roles in organic synthesis and industrial catalysis. [2][3][4][5][6][7][8][9] By studying the orbital interactions within these metal-carbon multiple bonds, including the factors that lead to Fischer-(electrophilic at carbon) versus Schrock-(nucleophilic at carbon) type carbenes and carbynes, researchers have been able to prepare complexes with desired modes of reactivity.…”

Section: Introductionmentioning

confidence: 99%

σ or π? Bonding interactions in a series of rhenium metallotetrylenes

et al. 2021

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Section: Introductionmentioning

confidence: 99%

σ or π? Bonding interactions in a series of rhenium metallotetrylenes

et al. 2021

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“…Figure 4 shows the 1 H NMR spectral regions used for the real time monitoring of substrate and product concentrations at different time intervals for experiment 4 as an example. The isomerization [27][28][29][30] of hex-1ene (1), 5-decene (5) and heptene (10) and the participation of these isomers, together with other metathesis by-products such as ethene (6), propene (4) and butene (8) in metathesis reactions, cannot be excluded. Certain resonances may thus be ascribed to the expected compounds and homologues thereof: the ddt corresponding to H-2 of hex-1-ene (1) may therefore also be ascribed to other terminal alkenes; the dd corresponding to H-1 of (E)-1-(4-methoxyphenyl)-1-hexene (3) may include H-1 of homologues with four or more carbons in the side chain, and the multiplet corresponding to H-5 of 5-decene (5) may include other internal alkene resonances [31,32].…”

Section: Figurementioning

confidence: 99%

“…In recent years, the CM methodology to form carbon-carbon double bonds employing Grubbs catalysts have been investigated extensively and numerous review articles summarize this [2,[4][5][6][7][8][9][10][11]. Cross-metathesis is a convenient synthetic approach to introduce a molecular fragment, often with a functional group, to a simple alkene to produce a valueadded compound.…”

Section: Introductionmentioning

confidence: 99%

1H NMR Analysis of the Metathesis Reaction between 1-Hexene and (E)-Anethole Using Grubbs 2nd Generation Catalyst: Effect of Reaction Conditions on (E)-1-(4-Methoxyphenyl)-1-hexene Formation and Decomposition

2021

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The metathesis of 1-hexene and (E)-anethole in the presence of Grubbs 2nd generation catalyst was monitored by in situ 1H NMR spectroscopy at different temperatures (15 °C, 25 °C, and 45 °C) and anethole mol fractions (XAnethole ≈ 0.17, 0.29, 0.5, 0.71, 0.83). Time traces confirmed the instantaneous formation of (E)-1-(4-methoxyphenyl)-1-hexene, the cross-metathesis product. A maximum concentration of (E)-1-(4-methoxyphenyl)-1-hexene is reached fairly fast (the time depending on the reaction conditions), and this is followed by a decrease in the concentration of (E)-1-(4-methoxyphenyl)-1-hexene due to secondary metathesis. The maximum concentration of (E)-1-(4-methoxyphenyl)-1-hexene was more dependent on the XAnethole than the temperature. The highest TOF (3.46 min−1) was obtained for the reaction where XAnethole was 0.16 at 45 °C. The highest concentration of the cross-metathesis product was however achieved after 6 min with an anethole mol fraction of 0.84 at 25 °C. A preliminary kinetic study indicated that the secondary metathesis reaction followed first order kinetics.

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“…Carbyne complexes, i.e., transition metal complexes with metal-carbon triple bonds, can be described as analogs of alkynes, whereas a transition metal replaces one of the sp carbons. They have attracted considerable attention because of their remarkable features and their significance as catalysts or reagents for various types of organic transformations [5][6][7][8][9][10][11]. Part of the reactivities of carbynes paralleled that of their organic parents, such as nucleophilic reactions, electrophilic reactions, photochemistry, oxidation and reduction, reactions with chalcogenides, reactions with unsaturated organic substrates (cycloadditions) and substitution on the α carbon (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in the Reactions of Cyclic Carbynes

Qian¹,

Ding²,

Du³

et al. 2020

Molecules

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The acyclic organic alkynes and carbyne bonds exhibit linear shapes. Metallabenzynes and metallapentalynes are six- or five-membered metallacycles containing carbynes, whose carbine-carbon bond angles are less than 180°. Such distortion results in considerable ring strain, resulting in the unprecedented reactivity compared with acyclic carbynes. Meanwhile, the aromaticity of these metallacycles would stabilize the ring system. The fascinating combination of ring strain and aromaticity would lead to interesting reactivities. This mini review summarized recent findings on the reactivity of the metal–carbon triple bonds and the aromatic ring system. In the case of metallabenzynes, aromaticity would prevail over ring strain. The reactions are similar to those of organic aromatics, especially in electrophilic reactions. Meanwhile, fragmentation of metallacarbynes might be observed via migratory insertion if the aromaticity of metallacarbynes is strongly affected. In the case of metallapentalynes, the extremely small bond angle would result in high reactivity of the carbyne moiety, which would undergo typical reactions for organic alkynes, including interaction with coinage metal complexes, electrophilic reactions, nucleophilic reactions and cycloaddition reactions, whereas the strong aromaticity ensured the integrity of the bicyclic framework of metallapentalynes throughout all reported reaction conditions.

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The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2018

Cited by 10 publications

References 1,313 publications

σ or π? Bonding interactions in a series of rhenium metallotetrylenes

σ or π? Bonding interactions in a series of rhenium metallotetrylenes

1H NMR Analysis of the Metathesis Reaction between 1-Hexene and (E)-Anethole Using Grubbs 2nd Generation Catalyst: Effect of Reaction Conditions on (E)-1-(4-Methoxyphenyl)-1-hexene Formation and Decomposition

Recent Advances in the Reactions of Cyclic Carbynes

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