An additional potential donor-bearing alkylidene-containing latent NHC–ruthenium-based catalyst for olefin metathesis polymerization

Sivanesan, Dharmalingam; Seo, Bongkuk; Lim, Choong‐Sun; Choi, Dongchen; Kim, Tae-Hee; Kim, Hyeon-Gook

doi:10.1039/c9py01952a

Cited by 10 publications

(10 citation statements)

References 39 publications

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“…Although, the crystal structure of LC-16 could not be determined, the J C−H coupling constant of 160. 6 Hz indicates that an anti-alkylidene with N-chelation is present. MOC1 crystallizes in the triclinic space group P1̅ , with a = 1025.46 (6) pm, b = 1951.56 (15) pm, c = 2372.1(2) pm; α = 72.382 (6), β = 79.241(6)°, γ = 75.826(5)°, and Z = 4 (Figure 6).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…6 Hz indicates that an anti-alkylidene with N-chelation is present. MOC1 crystallizes in the triclinic space group P1̅ , with a = 1025.46 (6) pm, b = 1951.56 (15) pm, c = 2372.1(2) pm; α = 72.382 (6), β = 79.241(6)°, γ = 75.826(5)°, and Z = 4 (Figure 6). Despite the high R value and standard deviation, the geometric parameters are sufficiently good to be discussed here.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Such approach substantially simplifies both the handling and the necessary equipment, since it avoids the mixing of catalyst, activator, and monomer for the in situ creation of a polymerization-active system. The synthesis of high-tech thermoset polymers from DCPD is an important industrial application of latent olefin metathesis catalysts . An ideal latent catalyst does not show catalytic activity in the presence of the monomer or substrate under storage conditions; however, quantitative and fast activation is desired exactly when and where it is needed.…”

Section: Introductionmentioning

confidence: 99%

“…The synthesis of high-tech thermoset polymers from DCPD is an important industrial application of latent olefin metathesis catalysts. 6 An ideal latent catalyst does not show catalytic activity in the presence of the monomer or substrate under storage conditions; however, quantitative and fast activation is desired exactly when and where it is needed. Latent catalysts should be tolerant toward all components of the polymerization mixture as well as toward decomposition or thermal degradation and, ideally, toward air.…”

Section: ■ Introductionmentioning

confidence: 99%

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Tuning the Latent Behavior of Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes in Dicyclopentadiene Polymerization

Momin¹,

Musso²,

Frey³

et al. 2021

Organometallics

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We report the synthesis of O- and N-chelated hexacoordinated molybdenum imido alkylidene N-heterocyclic carbene (NHC) bistriflate and pentacoordinated molybdenum imido alkylidene NHC monotriflate monoalkoxide complexes and their use as thermally latent and in some cases air-stable precatalysts in the ring-opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD). Introduction of electron-withdrawing and electron-donating groups at the O-chelated alkylidene ligand allowed for the tuning of both the onset temperature of polymerization (T onset) and the temperature of the exotherm maximum (T exo,max). In addition, N-chelated complexes were synthesized using easily available 2-vinylpyridine or 2-vinyl-N,N-dimethylaniline to yield five-membered and, for the first time, four-membered molybdenum imido alkylidene NHC chelates. With these precatalysts, T onset and T exo,max could be varied between 52 and 142 °C and between 99 and 174 °C, respectively.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Tuning the Latent Behavior of Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes in Dicyclopentadiene Polymerization

Momin¹,

Musso²,

Frey³

et al. 2021

Organometallics

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“…Notably, the introduction of methoxy (−OCH 3 ) and thioether (−SCH 3 ) groups in the catalyst did not induce latent behavior . Tethering an additional donor ligand using substituted pyridine in the ruthenium catalyst bearing an NHC and alkylidene ligands enhanced the latency behavior and the catalysts initiated polymerization at 60 °C . On the basis of the proven metathesis polymerization mechanism, the dissociation of the imine nitrogen in the alkylidene initiates polymerization.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular Hydrogen-Bond-Based Latent Initiator for Olefin Metathesis Polymerization

et al. 2021

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Latent olefin metathesis polymerization catalysts have enormous potential, as they provide access to thermoset polymers. However, developing a novel latent catalyst is difficult because the catalyst must be inactive at room temperature and completely convert the starting material to the product upon activation. Herein, we report the synthesis of a series of novel initiators 1–4 bearing an additional hydrogen donor that can form a weak hydrogen bond with the metal-bound chloride anion of the active species of an alkylidene-containing N-heterocyclic carbene (NHC)-Ru-based initiator, and their latent catalytic behavior was examined in the ring-opening olefin metathesis polymerization (ROMP) of dicyclopentadiene (DCPD) and cyclooctadiene (COD). The presence of intramolecular hydrogen bonds in initiators 1 and 2 facilitates latent polymerization, whereas the absence of intramolecular hydrogen bonds in initiators 3 and 4 allowed polymerization of DCPD at 30 °C. The TGA and DSC results for poly-DCPD (PDCPD) suggest that the intramolecular hydrogen bonding in initiators 1 and 2 did not alter the nature of the NHC-Ru-based initiator at 80 °C.

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A Simple Synthetic Route to [Rh(acac)(CO)(NHC)] Complexes: Ligand Property Diagnostic Tools and Precatalysts

et al. 2021

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An operationally simple, user and eco‐friendly synthetic protocol for the synthesis of [Rh(acac)(CO)(NHC)] complexes is described. Insights into the mechanism are provided using operando spectroscopy. The spectroscopic fingerprints of these complexes are correlated to NHCs reported electron‐donating descriptor values, highlighting a new strategy to evaluate carbenes’ electronic properties. An assessment of these complexes in catalytic applications is also reported, showing promising results in the catalytic hydrogenation of aromatic ketones.

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An additional potential donor-bearing alkylidene-containing latent NHC–ruthenium-based catalyst for olefin metathesis polymerization

Abstract: Introduction of an additional donor, by tethering substituted pyridine, in the alkylidene ligand of a NHC-based ruthenium complex initiates latent olefin metathesis polymerization.

Cited by 10 publications

References 39 publications

Tuning the Latent Behavior of Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes in Dicyclopentadiene Polymerization

Tuning the Latent Behavior of Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes in Dicyclopentadiene Polymerization

Intramolecular Hydrogen-Bond-Based Latent Initiator for Olefin Metathesis Polymerization

A Simple Synthetic Route to [Rh(acac)(CO)(NHC)] Complexes: Ligand Property Diagnostic Tools and Precatalysts

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