Density functional theory study of ring-chain equilibria for the cross-metathesis of cyclohexene and cis,cis-cycloocta-1,5-diene with functionalized olefins

Gutiérrez, Selena; Fulgencio, Arturo; Tlenkopatchev, Mikhail A.

doi:10.1016/j.jct.2005.06.004

Cited by 7 publications

(9 citation statements)

References 18 publications

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“…1 The computational modeling of the ring-chain equilibrium for the ring-opening cross-metathesis of cyclohexene (CH) with ethylene and carbonyl-containing olefins revealed that CH-ringopened products equilibrium is shifted toward the thermodynamically stable six-membered ring. 2 Such unreactive-in-ROMP rings can be prepared via ring-closing metathesis (RCM) of the appropriate compounds. Thus, ROMP-nonpolymerizable 4-methylcyclohexene has been prepared by RCM degradation of highly alternated butadiene-propylene copolymer.…”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, six-membered rings do not undergo ROMP due to their low strain energy . The computational modeling of the ring−chain equilibrium for the ring-opening cross-metathesis of cyclohexene (CH) with ethylene and carbonyl-containing olefins revealed that CH-ring-opened products equilibrium is shifted toward the thermodynamically stable six-membered ring . Such unreactive-in-ROMP rings can be prepared via ring-closing metathesis (RCM) of the appropriate compounds.…”

Section: Introductionmentioning

confidence: 99%

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Ring-Opening of Cyclohexene via Metathesis by Ruthenium Carbene Complexes. A Computational Study

and

Tlenkopatchev

2007

Organometallics

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Cyclohexene (CH) metathesis reaction mediated by the second-generation ruthenium alkylidene catalyst (IMesH2)(PCy3)CI2RuCHPh (1a), ruthenium ester carbene complexes (IMesH2)(PCy3)CI2RuCHCOOMe (1b), and (PCy3)2CI2RuCHCOOMe (1c), where IMesH2 is a 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene group, has been modeled at the PBE0/LACV3P**++//PBE0/LACVP* level of theory. The calculations revealed that the necessary condition for the catalyst to be active in CH ring-opening is the existence of a high-energy π-complex. It has been shown that the complex 4b complies with this condition, while the ruthenium alkylidene 4a does not. The higher reactivity of 1b compared to 1c can be rationalized in terms of better stabilization of the Ru center in transition states by the IMesH2 ligand.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Ring-Opening of Cyclohexene via Metathesis by Ruthenium Carbene Complexes. A Computational Study

and

Tlenkopatchev

2007

Organometallics

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“…Tlenkopatchev and his co-workers reported the molecular modeling of the distributions of cyclic and linear products in the ring-opening cross-metathesis of cis , cis -1,5-dimethyl-cycloocta-1,5-diene, cis , cis -1,6-dimethyl-cycloocta-1,5-diene, and cis , cis -cycloocta-1,5-diene with ethylene at 298.15 K using the B3LYP/6-31G(d,p) level of theory. , It was revealed that the ring–chain equilibrium constants were dependent on the nature of cyclic diene, in agreement with the reported experimental data by others. The computational modeling of ring–chain equilibria for the ring-opening cross-metathesis of cyclohexene with 1,2-dicarbomethoxy-ethylene, 1,4-dicarbomethoxy-but-2-ene (DCB), and ethylene demonstrated that the cyclohexene and ring-opened products tended to the thermodynamically stable six-membered ring, and the carbonyl-containing olefins could drive the cross metathesis with cis , cis -cycloocta-1,5-diene to the ring-opened products …”

Section: Modeling and Simulationmentioning

confidence: 99%

“…The computational modeling of ring−chain equilibria for the ring-opening cross-metathesis of cyclohexene with 1,2-dicarbomethoxy-ethylene, 1,4-dicarbomethoxy-but-2-ene (DCB), and ethylene demonstrated that the cyclohexene and ring-opened products tended to the thermodynamically stable six-membered ring, and the carbonyl-containing olefins could drive the cross metathesis with cis,cis-cycloocta-1,5-diene to the ring-opened products. 81 Since the early 1970s, Hummel started to research the computer simulation of metathesis reactions in order to elucidate the rubber structures. 82,83 Following with the analysis of the degraded products 84 and understanding the degradation mechanism, 85 the polymer degradation CM reaction has been widely investigated.…”

Section: ■ Modeling and Simulationmentioning

confidence: 99%

Olefin Metathesis Reaction in Rubber Chemistry and Industry and Beyond

Liu

2018

Ind. Eng. Chem. Res.

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The olefin metathesis reaction has showed promising application in rubber chemistry and industry in the last decades for the production of specialty rubbers (polyene rubbers, low-molecular-weight telechelic oligomers, hydrogenated diene-based rubbers, liquid rubbers, and other functional rubbers) and characterization and recycling of rubber products (waste tires or others) via ring-opening metathesis polymerization (ROMP) or the cross-metathesis (CM) degradation technique. Here, recent advances in both molecular modeling and experimental investigations of the olefin metathesis reaction in rubber chemistry and industry are reviewed, and the challenges of future applications are also prospected.

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“…1 Hence, ROMP has been limited to high strain energy monomers such as norbornenes, cyclooctadienes, and cyclobutenes. 1−3 However with recent developments and innovations, low strain cyclic olefins such as cyclohexene (CH), which traditionally is impractical for ROMP, 4 can be incorporated into alternating copolymers via ROMP (AROMP) 5−7 and cascade enyne metathesis polymerization. 8−10 When CH is combined with specific monomer types that undergo only a single metathesis cycle and do not homopolymerize, the monomers will cross-react to form precisely alternating copolymers.…”

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confidence: 99%

Long-Range Kinetic Effects on the Alternating Ring Opening Metathesis of Bicyclo[4.2.0]oct-6-ene-7-carboxamides and Cyclohexene

Boadi

Sampson

2023

ACS Org. Inorg. Au

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We report an investigation of rates of ruthenium-catalyzed alternating ring opening metathesis (AROM) of cyclohexene with two different Ru-cyclohexylidene carbenes derived from bicyclo[4.2.0]oct-6-ene-7-carboxamides (A monomer) that bear different side chains. These monomers are propylbicyclo[4.2.0]oct-6-ene-7-carboxamide and N-(2-(2-ethoxyethoxy)ethanylbicyclo[4.2.0]oct-6-ene-7-carboxamide. The amide substitution of these monomers directly affects both the rate of the bicyclo[4.2.0]oct-6-ene-7-carboxamide ring opening and the rate of reaction of the resulting carbene with cyclohexene (B monomer). The resulting Ru-cyclohexylidenes underwent reversible ring opening metathesis with cyclohexene. However, the thermodynamic equilibrium disfavored cyclohexene ring opening. Utilization of triphenylphosphine forms a more stable PPh3 ligated complex, which suppresses the reverse ring closing reaction and allowed direct measurements of the forward rate constants for formation of various A-B and A-B-A′ complexes through carbene-catalyzed ring-opening metathesis and thus gradient polymer structure-determining steps. The relative rate of the propylbicyclo[4.2.0]oct-6-ene-7-carboxamide ring opening is 3-fold faster than that of the N-(2-(2-ethoxyethoxy)ethanylbicyclo[4.2.0]oct-6-ene-7-carboxamide. In addition, the rate of cyclohexene ring-opening catalyzed by the propyl bicyclooctene is 1.4 times faster than when catalyzed by the ethoxyethoxy bicyclooctene. Also, the subsequent rates of bicyclo[4.2.0]oct-6-ene-7-carboxamide ring opening by propyl-based Ru-hexylidene are 1.6-fold faster than ethoxyethoxy-based Ru-hexylidene. Incorporation of the rate constants into reactivity ratios of bicyclo[4.2.0]amide-cyclohexene provides prediction of copolymerization kinetics and gradient copolymer structures.

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Density functional theory study of ring-chain equilibria for the cross-metathesis of cyclohexene and cis,cis-cycloocta-1,5-diene with functionalized olefins

Cited by 7 publications

References 18 publications

Ring-Opening of Cyclohexene via Metathesis by Ruthenium Carbene Complexes. A Computational Study

Ring-Opening of Cyclohexene via Metathesis by Ruthenium Carbene Complexes. A Computational Study

Olefin Metathesis Reaction in Rubber Chemistry and Industry and Beyond

Long-Range Kinetic Effects on the Alternating Ring Opening Metathesis of Bicyclo[4.2.0]oct-6-ene-7-carboxamides and Cyclohexene

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