Mono‐ and Bisionic Mo‐ and W‐Based Schrock Catalysts for Biphasic Olefin Metathesis Reactions in Ionic Liquids

Schowner, Roman; Elser, Iris; Tóth, Ferenc L.; Robé, Emmanuel; Frey, Wolfgang; Buchmeiser, Michael R.

doi:10.1002/chem.201802472

Cited by 15 publications

(12 citation statements)

References 65 publications

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“…For the imidazolinium chloride HO3 · HCl , however, complete 2-fold deprotonation was easily achieved under the same conditions (Figure S2 in the Supporting Information). Such selective deprotonation could be advantageous, since it offers an attractive access to cationically tagged alkylidyne complexes that might be used under biphasic conditions as realized with ionic olefin metathesis catalysts …”

Section: Synthesismentioning

confidence: 99%

Molybdenum and Tungsten Alkylidyne Complexes Containing Mono-, Bi-, and Tridentate N-Heterocyclic Carbenes

et al. 2019

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New tungsten and molybdenum alkylidyne complexes bearing mono-, bi-, and tridentate N-heterocyclic carbenes (NHCs) have been synthesized. Formation of unprecedented structures in complexes bearing N-tert-butyl substituents on the imidazol(in)-2-ylidene was observed, leading to molybdenum complexes containing an abnormal carbene (Mo-4) and a bridging O,C,C-pincer ligand (Mo-10) and to a tungsten complex containing a cationic imidazolinium-tagged alkoxide forming an inner salt with an anionic tungsten center (W-5). Both the abnormal carbene binding in Mo-4 and the O,C,C-pincer-type structure of Mo-10 were confirmed by singlecrystal X-ray analysis, and the proposed structure of W-5 is supported by the single-crystal X-ray structure of a minor byproduct (W-8) formed during the synthesis of W-4, displaying the aforementioned inner-salt-like structure. The novel alkylidyne complexes were also investigated for their capability to form a previously postulated quasi-cationic species with a weakly coordinating anion (WCA) during the alkyne homometathesis of 1phenyl-1-propyne. Overall, incorporation of bidentate and strongly σ donating NHCs as well as introduction of better leaving groups did not lead to the expected increase in catalytic activity. Despite identical ligand spheres, changing from molybdenum to tungsten led to complete loss of activity in the bidentate systems.

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Section: Synthesismentioning

confidence: 99%

Molybdenum and Tungsten Alkylidyne Complexes Containing Mono-, Bi-, and Tridentate N-Heterocyclic Carbenes

et al. 2019

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“…Despite their long history of more than one century, ionic liquids (ILs) have gained increasing attention in the last two decades. They have been utilized in many different applications, such as batteries, , fuel cells, supercapacitors, extraction, electrodeposition, liquid crystals, , solvents, , including large-scale industrial processes, for carbon dioxide capture, − in catalysis, ,− as explosives and rocket fuel, and even for building telescope mirrors . One milestone in the readvent of ILs probably happened in 2002, when it was discovered that certain imidazolium-based ILs are able to dissolve cellulose .…”

Section: Introductionmentioning

confidence: 99%

Triazolium-Based Ionic Liquids: A Novel Class of Cellulose Solvents

et al. 2019

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We present first results on triazolium-based ionic liquids (ILs) as a novel class of nonderivatizing solvents for cellulose. Despite their chemical similarity to imidazolium cations, the 1,2,3-triazolium cation lacks the isolated ring proton, leading to reduced formation of N-heterocyclic carbenes (NHCs) and therefore to lower reactivity and less unwanted side reactions. We synthesized six ILs based on 1,2,3-triazolium and 1,2,4-triazolium cations. The acetates are room-temperature ionic liquids and dissolve a similar amount of cellulose as the corresponding imidazolium salt. From NMR spectroscopy of the solution, we rule out polymer degradation. The cellulose solubility rises with increasing anion basicity, while being almost independent of the cation. We perform molecular dynamics simulations and compute enthalpies of solvation, which quantitatively fit the experimental solubilities. Trajectory analysis reveals strong hydrogen bonds between acetate anions and cellulose hydroxyl groups, while the cations do not form strong hydrogen bonds with cellulose. Thus, the simulations provide an atomistic explanation of our experimental observations.

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“…ILs are widely exploited in chemistry, nanotechnology [64,65], engineering [66][67][68], biotechnology [69][70][71][72][73][74], pharmaceutical industries [75][76][77][78][79][80]. ILs have many exertion like as natural fibers processing, carbon dioxide capture [81][82][83], separation, battery [84,85], biofuel formation, extraction [86], biological activities, solvents [87,88], catalysis [89][90][91][92], fuel cells [93] and biomedical uses [94]. Several reports have included a total or partial degradation of the epoxy thermoset polymers as well as utilized the end productions for making functional materials for various applications [95][96][97][98].…”

Section: Applications Of Ionic Liquidsmentioning

confidence: 99%

A Review of Green Solvent Ionic Liquids: As a Future Solvent

Tomar¹,

Jain²

2022

JASR

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Currently, chemists seem more fascinated with exploiting less hazardous green solvent ionic liquids for countering the detrimental consequence of organic solvents on the environment. Ordinarily, ionic liquids having salt-like structures comprise cations and anions. Ionic liquids alleviate various enzyme-catalyzed reactions having excellent yields, increasing capacities and functions, enhancing recyclability, increasing stability, recovery, and cost-effectiveness, and these are cardinal elements for applications in industry. Furthermore, growing nanotechnology, polymer, electrochemistry, environmental chemistry, pharmaceutical medicinal chemistry or pharmaceutical chemistry, and biochemistry in the area of ionic liquids have been flourished among investigators. Ionic liquids-supported materials and techniques are excellent for efficient and sustainable procedures. Because of their assignment as designer solvents, through which the physiochemical dimensions of an Ionic liquid can be adjusted for better functioning for peculiar applications. The review delivers the gradual improvement, growth or development, or progress and prospects of ionic liquids and their physicochemical properties as well as examples of applications in a unified fashion.

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Mono‐ and Bisionic Mo‐ and W‐Based Schrock Catalysts for Biphasic Olefin Metathesis Reactions in Ionic Liquids

Cited by 15 publications

References 65 publications

Molybdenum and Tungsten Alkylidyne Complexes Containing Mono-, Bi-, and Tridentate N-Heterocyclic Carbenes

Molybdenum and Tungsten Alkylidyne Complexes Containing Mono-, Bi-, and Tridentate N-Heterocyclic Carbenes

Triazolium-Based Ionic Liquids: A Novel Class of Cellulose Solvents

A Review of Green Solvent Ionic Liquids: As a Future Solvent

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