Olefin Metathesis

Calderon, Nissim; Lawrence, J.P.; Ofstead, E. A.

doi:10.1016/s0065-3055(08)60329-9

Cited by 168 publications

(21 citation statements)

References 74 publications

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“…One can consider as a normal case the reactivity of double bonds in low molecular olefins such as 4-octene or polymers such as 1,4-poly(butadiene). In comparison strained cycloolefins such as norbornene react considerably faster [24]. Substituted linear olefins react more slowly, the reactivity being dependent on the distance between the functional group and the double bond [24][25][26][27].…”

Section: A) Reactivity Of the C= C Double Bonds In Olefin Metathesismentioning

confidence: 99%

“…In comparison strained cycloolefins such as norbornene react considerably faster [24]. Substituted linear olefins react more slowly, the reactivity being dependent on the distance between the functional group and the double bond [24][25][26][27]. Lower reactivity is observed in the metathesis degradation of polymers with substituents neighbouring the double bonds [19,20,27,28].…”

Section: A) Reactivity Of the C= C Double Bonds In Olefin Metathesismentioning

confidence: 99%

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Some aspects of the synthesis and characterization of special polymers and oligomers by olefin metathesis

Stelzer

Graiman

Hummel

1982

Colloid & Polymer Sci

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Homopolymers of 2-norbornene and 2,3-bis(trifluoromethyl)-2,5-norbornadiene and copolymers of these bicyclic olefins with 1,5-cyclooctadiene and cyclopentene were prepared via ring opening metathesis polymerization. The molecular weight distributions of the polymers were estimated by gel permeation chromatography. The polymers were degraded in a cross metathesis reaction with E-4-octene; only poly[2,3-bis(trifluoromethyl),2,5-norbornadiene] was not degradable. All reactions were carried out with WC16/(CH3)4Sn as the catalyst system. The low molecular cyclic oligomers in the polymerization mixtures and the degradation products were analyzed by gas chromatography and identified using a gas chromatography/mass spectrometry coupling. The degradation experiments show reactivity differences for the double bonds situated in the polymer backbone. On the basis of these differences and the fact that this is the first time that a metathesis degradation of such polymers has been reported, the consequences on the ring opening metathesis copotymerization of cycloolefins are discussed in general terms, leading to some new aspects in the planning of the synthesis of special copolymers and oligomers.

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Section: A) Reactivity Of the C= C Double Bonds In Olefin Metathesismentioning

confidence: 99%

Section: A) Reactivity Of the C= C Double Bonds In Olefin Metathesismentioning

confidence: 99%

Some aspects of the synthesis and characterization of special polymers and oligomers by olefin metathesis

Stelzer

Graiman

Hummel

1982

Colloid & Polymer Sci

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“…Dies ist wegen der fraws-Stellung der koordinierten Olefine im (^2-01efin)2M(C0)4 auch verständlich, so daß dieser Komplextyp als Zwischenprodukt für die metallkatalysierte Photodimerisierung [21,22] oder als Modellverbindung für die Olefinmetathese [23,24] kaum in Betracht kommt.…”

Section: Schlußbemerkungunclassified

Bis (η²-olefin) tetracarbonylwolfram- und -molybdän-Komplexe: photochemische Synthese, Struktur und dynamisches Verhalten / Bin (η²-olefin)tetracarbonyltungsten and -molybdenum Complexes: Photochemical Synthesis, Structure and Fluxional Behaviour

Grevels¹,

Lindemami²,

Benn³

et al. 1980

Zeitschrift Für Naturforschung B

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“…deux amorceurs au niveau d'un schema reactionDepuis les premiers exemples de la reaction de metathese d'olefines en catalyse heterogene ou homogene (1,2), les travaux sur cette reaction sont exposes periodiquement dans un certain nombre de mises au point (3)(4)(5)(6)(7)(8)(9)(10). Les alcenes cycliques presentent un inter& particulier et l'etude, en catalyse homogene, du mecanisme de la polymerisation est toujours d'actualite (1 1-15).…”

Section: Introductionunclassified

Polymérisation du norbornène par des amorceurs au ruthénium. Etude cinétique de la réaction

Taniélian¹,

Kiennemann²,

Ösparpucu³

1980

Can. J. Chem.

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The kinetic parameters for the polymerisation reaction of norbornene with RuCl3•3H2O, and RuCl2(PΦ3)3 using homogeneous catalysis have been determined (first-order with respect to two initiators, zero-order with respect to the monomer with RuCl3•3H2O, and variable order with RuCl2(PΦ3)3: Ea 6.2 kcal/mol for RuCl2(PΦ3)3 and 22.8 for RuCl3•3H2O) and leads us to propose different reaction mechanisms for the polymerisation starting from the two initiators, at least for the initiation step. With RuCl2(PΦ3)3 the slow step of the reaction is the metathesis whereas with RuCl3•3H2O the slow step is a ligand exchange at the initiator involving solvent (alcohol) by a dissociative or associative mechanism. This slow step is confirmed by a study of varying alcohol concentration and initiator aging. [Journal translation]

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Olefin Metathesis

Cited by 168 publications

References 74 publications

Some aspects of the synthesis and characterization of special polymers and oligomers by olefin metathesis

Some aspects of the synthesis and characterization of special polymers and oligomers by olefin metathesis

Bis (η²-olefin) tetracarbonylwolfram- und -molybdän-Komplexe: photochemische Synthese, Struktur und dynamisches Verhalten / Bin (η²-olefin)tetracarbonyltungsten and -molybdenum Complexes: Photochemical Synthesis, Structure and Fluxional Behaviour

Polymérisation du norbornène par des amorceurs au ruthénium. Etude cinétique de la réaction

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Olefin Metathesis

Cited by 168 publications

References 74 publications

Some aspects of the synthesis and characterization of special polymers and oligomers by olefin metathesis

Some aspects of the synthesis and characterization of special polymers and oligomers by olefin metathesis

Bis (η2-olefin) tetracarbonylwolfram- und -molybdän-Komplexe: photochemische Synthese, Struktur und dynamisches Verhalten / Bin (η2-olefin)tetracarbonyltungsten and -molybdenum Complexes: Photochemical Synthesis, Structure and Fluxional Behaviour

Polymérisation du norbornène par des amorceurs au ruthénium. Etude cinétique de la réaction

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Bis (η²-olefin) tetracarbonylwolfram- und -molybdän-Komplexe: photochemische Synthese, Struktur und dynamisches Verhalten / Bin (η²-olefin)tetracarbonyltungsten and -molybdenum Complexes: Photochemical Synthesis, Structure and Fluxional Behaviour