Propagation and termination steps in Rh-mediated carbene polymerisation using diazomethane

Franssen, Nicole M. G.; Finger, Markus; Reek, Joost N. H.; Bruin, Bas de

doi:10.1039/c2dt32584e

Cited by 12 publications

(12 citation statements)

References 25 publications

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“…One of the characteristic infrared absorption peak of the planar conguration of O]C-CHN 2 group in a-diazo carbonyl compounds such as EDA was detected at 2110 cm À1 and no absorption sign was recorded with the products from the CP of EDA at the range of 2000-2200 cm À1 in our investigation. 39,40 The intensity of the absorption peak at 2110 cm À1 is expressed by its area (S) which is assumed to follow the Beer-Lambert law (eqn ( 2)). 37…”

Section: Resultsmentioning

confidence: 99%

“…36,38 But the two stages combined to one for Cat-1 system. The induction process of the Rh-catalyst was proved by the homopolymerization of EDA, 39 which involved with the nitrogen-releasing of EDA and led to the formation of several active species with different structures and activities. 40,41 Moreover, mechanism studies by these previous investigations suggest that the active species maybe the "real catalyst" for the formation of high molecular weight polymer in the homopolymerization of EDA.…”

Section: Rh-catalyst Mediated Carbethoxycarbene Polymerizationsmentioning

confidence: 99%

“…40,41 Moreover, mechanism studies by these previous investigations suggest that the active species maybe the "real catalyst" for the formation of high molecular weight polymer in the homopolymerization of EDA. 36,39 From eqn (4)-( 6) the general rate equation of Rh-mediated CP is summarized as eqn (7) and the simplied processes of CP with one and two ln[1/(a À x)]-time curves are presented by Fig. 2.…”

Section: Rh-catalyst Mediated Carbethoxycarbene Polymerizationsmentioning

confidence: 99%

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Kinetic study of carbene polymerization of ethyl diazoacetate by palladium and rhodium catalysts

Xiao

et al. 2014

RSC Adv.

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Kinetic studies of the carbene polymerization of ethyl diazoacetate (EDA) by palladium (Pd) or rhodium (Rh) catalysts were investigated by real-time Fourier transform infrared (FTIR) spectroscopy. Both (L-prolinate) Rh I (1,5-cyclooctadiene) and (L-prolinate)Rh I (2,5-norbornadiene) mediated EDA polymerization were proved to be first order reactions, suggesting that the formation of "Rh-carbenoid" is the rate determining step. The activation energy (11.24 kJ mol À1 ) of the polymerization of "carbenes" generated from EDA with (L-prolinate)Rh I (1,5-cyclooctadiene) as the catalyst was calculated from kinetic data via the Arrhenius equation. On the other hand, the polymerizations of EDA catalyzed by three kinds of Pdcatalysts were revealed as zero order reactions, suggesting that the rate determining step involves the formation of an EDA-Pd transition state complex through a coordinated step. Refilling more EDA to the (bis(acetonitrile)dichloropalladium)-mediated carbene polymerization system did not change the reaction order. The rate constant increases gradually with the increase of the dosage of the catalyst and decreases with the cycle-index, which proves the formation of "EDA-Pd transition state complex" and the propagating species with Pd-C bonds at the end of the polymer chain.

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Section: Resultsmentioning

confidence: 99%

Section: Rh-catalyst Mediated Carbethoxycarbene Polymerizationsmentioning

confidence: 99%

Section: Rh-catalyst Mediated Carbethoxycarbene Polymerizationsmentioning

confidence: 99%

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Kinetic study of carbene polymerization of ethyl diazoacetate by palladium and rhodium catalysts

Xiao

et al. 2014

RSC Adv.

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“…1,5-cyclooctadiene (cod) derivatives) under the applied reaction conditions. 267,277,279 These findings are expected to lead to future improvements of this approach in terms of yields, initiation efficiencies of the catalysts and in the synthesis of stereoregular polymers with different tacticities. This clearly indicates that this new reaction has not yet been exploited at its full potential.…”

Section: Carbene Polymerisationmentioning

confidence: 91%

Synthesis of functional ‘polyolefins’: state of the art and remaining challenges

2013

Self Cite

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Functional polyolefins (i.e., polyethene or polypropene bearing functional groups) are highly desired materials, due to their beneficial surface properties. Many different pathways exist for the synthesis of these materials, each with its own advantages and drawbacks. This review focuses on those synthetic pathways that build up a polymer chain from ethene/propene and functionalised polar vinyl monomers. Despite many recent advances in the various fields of olefin polymerisation, it still remains a challenge to synthesise high molecular-weight copolymers with tuneable amounts of functional groups, preferably with consecutive insertions of polar monomers occurring in a stereoselective way. To overcome some of these challenges, polymerisation of alternative functionalised monomers is explored as well.

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“…The deviations are likely resulting from an imperfect description of the metal-olefin interactions with density functional theory (and thereby the energy separation between the SOMO and the filled orbitals), which has also been noted for some other group-9 transition metal systems. [18] …”

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confidence: 99%

[Ni(cod)₂][Al(OR^F)₄], a Source for Naked Nickel(I) Chemistry

et al. 2015

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The straightforward synthesis of the cationic, purely organometallic NiI-salt [Ni(cod)2]+[Al(ORF)4]– was realized through a reaction between Ni(cod)2 and Ag[Al(ORF)4]. Crystal structure, EPR, XANES and cyclic voltammetry confirmed the presence of a homoleptic NiI-olefin complex. Weak interactions between the metal centre, the ligands and the anion provide a good starting material for further cationic NiI-chemistry.

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Propagation and termination steps in Rh-mediated carbene polymerisation using diazomethane

Abstract: Propagation and termination steps in Rh-mediated carbene polymerisation using diazomethane Franssen, N.M.G.; Finger, M.; Reek, J.N.H.; de Bruin, B.

Cited by 12 publications

References 25 publications

Kinetic study of carbene polymerization of ethyl diazoacetate by palladium and rhodium catalysts

Kinetic study of carbene polymerization of ethyl diazoacetate by palladium and rhodium catalysts

Synthesis of functional ‘polyolefins’: state of the art and remaining challenges

[Ni(cod)₂][Al(OR^F)₄], a Source for Naked Nickel(I) Chemistry

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Propagation and termination steps in Rh-mediated carbene polymerisation using diazomethane

Abstract: Propagation and termination steps in Rh-mediated carbene polymerisation using diazomethane Franssen, N.M.G.; Finger, M.; Reek, J.N.H.; de Bruin, B.

Cited by 12 publications

References 25 publications

Kinetic study of carbene polymerization of ethyl diazoacetate by palladium and rhodium catalysts

Kinetic study of carbene polymerization of ethyl diazoacetate by palladium and rhodium catalysts

Synthesis of functional ‘polyolefins’: state of the art and remaining challenges

[Ni(cod)2][Al(ORF)4], a Source for Naked Nickel(I) Chemistry

Contact Info

Product

Resources

About

[Ni(cod)₂][Al(OR^F)₄], a Source for Naked Nickel(I) Chemistry