Anionic polymerization in the gas-phase cluster of 2-chloroacrylonitrile

Tsukuda, Tatsuya; Kondow, Tamotsu

doi:10.1021/j100193a001

Cited by 20 publications

(31 citation statements)

References 6 publications

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“…Meanwhile, considerable effort has been devoted to the investigation of these ion−molecule reactions in the cluster regime − as well. This has been prompted by the recognition that interrogating clusters provides a way of studying the energetics and dynamics of intermediate states of matter as cluster systems evolve from the gas toward the condensed state .…”

Section: Introductionmentioning

confidence: 99%

Intracluster Polymerization Reactions of Alkene Cluster Ions

et al. 1997

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The unimolecular dissociation dynamics of selected alkene cluster ions (ethene, propene, 1-butene, trans-2butene, and cis-2-butene) and their fast fragment ions has been investigated using a reflectron time-of-flight mass spectrometer. These ions were prepared by the supersonic expansion of a premixed sample gas containing 20% alkene in Ar, followed by multiphotoionization (MPI) using a Ti:sapphire femtosecond laser. From the unimolecular decomposition patterns of all the ions investigated, we conclude that after photoionization a radical cation initiated intracluster polymerization takes place in these cluster ions. But, due to steric hindrance, it does not continue indefinitely as the cluster size increases. For ethene, pentamerization can be observed, and for propene, trimerization; while in the case of the three isomeric butenes, 1-butene is partially trimerized and only dimerization is observed in 2-butene.

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Section: Introductionmentioning

confidence: 99%

Intracluster Polymerization Reactions of Alkene Cluster Ions

et al. 1997

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“…Low-energy electron attachment to neutral clusters of 2-chloroacrylonitrile (CAN) creates a complex distribution of anions consistent with the occurrence of an intracluster polymerization reaction. 1 Previously, we proposed that the key to understanding the polymerization mechanism lay in the structure of the CANmonomer anion. We had investigated the ion using photofragmentation techniques and observed CANfragmenting at 2.33 eV, yielding primarily Clwith a small amount of [H2C=CCN]-, indicating that CANhas a dissociative low-lying electronic state.2 This was slightly surprising since similar molecules such as acrylonitrile (H2C=CHCN) have low electron affinities (< 1 eV),3 so that electron detachment would be expected to occur well below such an absorption band.…”

Section: Introductionmentioning

confidence: 99%

Characterization of the 2-Chloroacrylonitrile Negative Ion Using Photoelectron and Photofragmentation Spectroscopies

Ichihashi¹,

Hirokawa²,

Tsukuda³

et al. 1995

J. Phys. Chem.

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We describe the spectroscopic characterization of the anions produced by low-energy electron attachment to neutral clusters of 2-chloroacrylonitrile (CAN). The photoelectron spectrum of the CAN-anion is markedly similar to that of the ion-molecule complex, C1-CAN, implying that the excess charge in CAN-is localized on the chlorine atom. A b initio calculations support this inference, indicating that upon electron attachment CAN-rearranges to a novel distonic ion-radical complex, Cl-*HZC=CCN. The photoabsorption spectrum of the anion is consistent with a charge transfer transition to an excited state, Cl*[HzC%CN]-*. This chromophore dominates the photofragmentation chemistry of CAN-, with the dominant photofragments at all wavelengths being C1-(presumably formed by reverse charge transfer relaxation of the excited state) and [HzC-CCNI-. The propensity of neutral clusters of CAN to polymerize upon electron attachment is readily explicable in view of the proposed ion-radical structure of CAN-.

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“…28 A similar anionic polymerization and sequential elimination of HC1 have been observed in electron attachment onto clusters of 2-chloroacrylonitrile (CAN). 29 In a photodissociation study on dimeric anions, [(CAN)2 -mHCl]*-(m = 0-2), the elimination of one HC1 molecule is the dominant channel. 30 In the electron attachment to clusters of methyl acrylate (MA), the intensity of (M A) 5-is enhanced at a higher stagnation pressure and explained by chemical-bond formation in the cluster anion; i.e., intracluster anionic polymerization occurs in (MAV-.31 These mass spectroscopic studies on the intracluster ionic polymerization reactions have suggested that (i) the formation of stable ions leads to the termination of the chain-propagation sequence of the polymerization and (ii) the evaporation of unreacted monomers and/or the elimination of neutral species are the main relaxation pathways for producing the nascent polymeric ions in the gas phase.…”

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confidence: 99%