Nickel(0)-Catalyzed [2 + 2 + 2 + 2] Cycloadditions of Terminal Diynes for the Synthesis of Substituted Cyclooctatetraenes

Wender, Paul A.; Christy, Justin P.

doi:10.1021/ja0763044

Cited by 64 publications

(36 citation statements)

References 19 publications

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“…Accordingly, the infinite chain represents a zigzag-shape. This is different from the other reported clusters [24,25,27], the insolubleness of which prevents further study of taking them as the building blocks. Disordered Ni (6) and Ni(6A) attach to the zigzag chains by using Ni-O bonds, and make chain-like structure of compound 1 more stable.…”

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confidence: 74%

“…POMs are employed as the catalysts in oxidation reactions [19][20][21], while also as the catalysts, nickel containing compounds have attracted much attention during the past decade [22][23][24][25]. So we make efforts to assemble the welldefined POMs based on Keggin unit and nickel directly under hydrothermal conditions via introducing the organic amine as a structure direct reagent.…”

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confidence: 99%

“…the past decade [22][23][24][25]. So we make efforts to assemble the welldefined POMs based on Keggin unit and nickel directly under hydrothermal conditions via introducing the organic amine as a structure direct reagent.…”

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confidence: 99%

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Hydrothermal synthesis, structure characterization and catalytic property of a zigzag chain structural cluster compound built on the novel tetra-capped and centered by NiII

Yan

et al. 2011

Inorganic Chemistry Communications

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confidence: 99%

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Hydrothermal synthesis, structure characterization and catalytic property of a zigzag chain structural cluster compound built on the novel tetra-capped and centered by NiII

Yan

et al. 2011

Inorganic Chemistry Communications

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“…The syntheses of dichloro-(glyme)nickel and dibromo(glyme)nickel are also described and elementary analyses indicated that the nickel ion is in this case tetracoordinate, contrary to compound 3. Dibromo(glyme)nickel finds it application in the catalysis of [2+2+2+2] cycloadditions of terminal diynes for the synthesis of substituted cyclooctatetraenes [58]. Compound 3 does not show catalytic activity.…”

Section: Compound [Cis-nii 2 (Glyme) 2 ] (3)mentioning

confidence: 99%

Polyether Adducts of d‐Block Metal Compounds as Starting Materials for New Cluster Compounds

Crochet

Fromm

2010

Zeitschrift anorg allge chemie

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Abstract. New crystalline cobalt, nickel, zinc, and mercury halide adducts with polyethers as ligands have been isolated, characterized, and identified as [Co(μ-Cl) IntroductionWe are interested in molecular compounds, especially oxygen donor adducts of metal halides, because they are useful as starting materials in the synthesis of low-dimensional polymeric compounds, i.e. clusters, and polymers or metal organic frameworks [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. Indeed, since more than two decades, metal aggregates are used in the low-cost synthesis of superconductors and other oxide materials based on the sol-gel technique or as volatile precursors in the MOCVD (Metal Organic Chemical Vapor Deposition) process [3,11,13,[17][18][19][20][21]. One of the major problems of the synthesis of organo-metal(II) compounds, including the alkaline earth metal ions, is their possible tendency to form insoluble polymers [21][22][23][24], on one hand due to their low metal oxidation state M II , which only allows two anionic ligands, and on the other hand, their ionic radii, which demand a high coordination number. A parry to prevent a high degree of oligomerization is the use of neutral Lewis-coordinating ligands such as monodentate THF or multidentate polyether ligands, which avoid any further "metal-metal contacts" via bridging ligands, saturating the metal cation. However, the chemistry of such metal halide or pseudo-halide adducts with neutral Lewis-coordinating ligands (usually non-polar aprotic solvents) is still not systematically studied.Compounds that have so far been isolated in the class of molecular species are, for instance, the zero-dimensional com- Published in =HLWVFKULIW I U DQRUJDQLVFKH XQG DOOJHPHLQH &KHPLH ± which should be cited to refer to this work.

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“…2 Herein we propose a new strategy for controling the reactions which proceed through formation of a dimeric metal intermediate: Isolation (or immobilization) of the metal-catalyst 35 into an ionic liquid (IL) 3 phase in an IL/usual organic solvent biphasic system which can separate the catalyst from the employed substrate and maintain a high catalyst concentration in the IL phase throughout the reaction, a situation which might be favorable for reactions via a dimeric metal intermediate and corresponding COTs catalyzed by a (DME)NiBr 2 /Zn [DME = 1,2-dimethoxyethane] reagent in THF-H 2 O, where reaction with a large amount of catalyst loading (20~40 mol%) realized highly selective production of COTs against co-production of [2+2+2] cycloadducts. 6 The results were rationalized by assuming the 55 dimeric mechanism that Wilke suggested.Cyclooctatetraenes (COTs) are of interest as ligands capable of coordinating to various metal atoms and electron transporting components in organic light-emitting devices, and especially as precursors for polyacetylenes in the ring-opening metathesis 60 polymerization (ROMP) reaction. 7 Efforts, therefore, have been made in developing methods for synthesizing COTs.…”

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Selective dimerization of 1,6-diynes catalyzed by ionic liquid-supported nickel complexes in an ionic liquid/toluene biphasic system

et al. 2009

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A NiCl 2 -6H 2 O/Zn reagent with a 2-aryliminomethylpyridine ligand catalyzed cyclization/polymerization of 1,6-diynes mainly to yield the corresponding poly(1,3-butadienylene) compounds, 10 whereas, NiBr 2 -3H 2 O/Zn with use of 3-(2-(2-methoxyethoxy)-ethyl)-1-methyl-1H-imidazol-3-ium bromide as a ligand converted 1,6-diynes to the corresponding annulated 1,3,5,7-cyclooctatetraenes in a biphasic solvent system consisting of toluene and an ionic liquid. 15For homogeneous metal-catalyzed reactions, a bimetallic or bimolecular cooperative mechanism has often been proposed, where a dimerization of the metal species or dimeric interaction of the metal species plays a critical role: 1 Many cases have been postulated in which a bimetallic or bimolecular mechanism is 20 involved as a major course for effective, selective production of the desired compound. Meanwhile, the reverse case has also been reported in which dimerization of the metal species deactivates the catalyst by forming stable, coordinatively saturated, inert complexes and furthers decomposition by disproportionation. In 25 this context, isolating the catalyst to a solid phase from a solution phase by immobilization onto polymeric supports or inorganic materials is a versatile means not only for avoiding the formation of dimeric metal molecules thereby deactivating and decomposing the catalyst but also for increasing the catalyst 30 reactivity and selectivity via a bimetallic or bimolecular mechanism. 2 Herein we propose a new strategy for controling the reactions which proceed through formation of a dimeric metal intermediate: Isolation (or immobilization) of the metal-catalyst 35 into an ionic liquid (IL) 3 phase in an IL/usual organic solvent biphasic system which can separate the catalyst from the employed substrate and maintain a high catalyst concentration in the IL phase throughout the reaction, a situation which might be favorable for reactions via a dimeric metal intermediate and corresponding COTs catalyzed by a (DME)NiBr 2 /Zn [DME = 1,2-dimethoxyethane] reagent in THF-H 2 O, where reaction with a large amount of catalyst loading (20~40 mol%) realized highly selective production of COTs against co-production of [2+2+2] cycloadducts. 6 The results were rationalized by assuming the 55 dimeric mechanism that Wilke suggested.Cyclooctatetraenes (COTs) are of interest as ligands capable of coordinating to various metal atoms and electron transporting components in organic light-emitting devices, and especially as precursors for polyacetylenes in the ring-opening metathesis 60 polymerization (ROMP) reaction. 7 Efforts, therefore, have been made in developing methods for synthesizing COTs. 8 Of the existing methods, the transition metal-catalyzed [2+2+2+2] cycloaddition of alkynes can be considered one of the most attractive and direct. 65During the course of studying the transition metal-catalyzed cycloisomerization of alkynes, 9 we found that a 2-(aryliminomethyl)pyridine/NiCl 2 -6H 2 O/Zn reagent catalyzed cycloaddition of diethyl dipropargylmalo...

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Nickel(0)-Catalyzed [2 + 2 + 2 + 2] Cycloadditions of Terminal Diynes for the Synthesis of Substituted Cyclooctatetraenes

Cited by 64 publications

References 19 publications

Hydrothermal synthesis, structure characterization and catalytic property of a zigzag chain structural cluster compound built on the novel tetra-capped and centered by NiII

Hydrothermal synthesis, structure characterization and catalytic property of a zigzag chain structural cluster compound built on the novel tetra-capped and centered by NiII

Polyether Adducts of d‐Block Metal Compounds as Starting Materials for New Cluster Compounds

Selective dimerization of 1,6-diynes catalyzed by ionic liquid-supported nickel complexes in an ionic liquid/toluene biphasic system

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