“…A wide range of studies concerning acrylonitrile in various environments and phases have been carried out during the last decades [6][7][8][9][10][11][12][13] and although many investigations concerning the dissociation of singly charged acrylonitrile have been published, much less is known about the dissociation processes of doubly charged acrylonitrile. 14 In this paper the dissociation processes of acrylonitrile dications are studied using photoelectron-photoion-photoion coincidence ͑PEPI-PICO͒ spectroscopy ͑see, e.g., Refs.…”
Dissociation of acrylonitrile into pairs of cations and neutral fragments following molecular core ionization was investigated using the photoelectron-photoion-photoion coincidence (PEPIPICO) technique. The fragment ion mass spectra were recorded in coincidence with the carbon 1s photoelectrons. Deuterated and (13)C-substituted samples were used for resolving fragment mass ambiguities. Slope analysis of the PEPIPICO patterns was used in determining the fragment separation sequences in case of multiparticle processes. The results show that there are several fragmentation channels producing a wide range of charged coincident fragments. The dynamics of the dominant fragmentation processes is investigated in detail.
“…A wide range of studies concerning acrylonitrile in various environments and phases have been carried out during the last decades [6][7][8][9][10][11][12][13] and although many investigations concerning the dissociation of singly charged acrylonitrile have been published, much less is known about the dissociation processes of doubly charged acrylonitrile. 14 In this paper the dissociation processes of acrylonitrile dications are studied using photoelectron-photoion-photoion coincidence ͑PEPI-PICO͒ spectroscopy ͑see, e.g., Refs.…”
Dissociation of acrylonitrile into pairs of cations and neutral fragments following molecular core ionization was investigated using the photoelectron-photoion-photoion coincidence (PEPIPICO) technique. The fragment ion mass spectra were recorded in coincidence with the carbon 1s photoelectrons. Deuterated and (13)C-substituted samples were used for resolving fragment mass ambiguities. Slope analysis of the PEPIPICO patterns was used in determining the fragment separation sequences in case of multiparticle processes. The results show that there are several fragmentation channels producing a wide range of charged coincident fragments. The dynamics of the dominant fragmentation processes is investigated in detail.
“…Two early examples (eqs 3 and 4) and two recent examples (eqs 5 and 6) are shown. The catalytic linear dimerization of acrylonitrile reported in the late 1960s has been recently suggested to involve the oxidative addition of a C−H bond β to the CN group onto the ruthenium, to give an intermediate such as 2 (eq 3). …”
The cleavage and addition of ortho C-H bonds in various aromatic compounds such as ketones, esters, imines, imidates, nitrile, and aldehydes to olefins and acetlylenes can be achieved catalytically with the aid of ruthenium catalysts. The reaction is generally highly efficient and useful in synthetic methods. The coordination to the metal center by a heteroatom in directing groups such as carbonyl and imino groups is the key. The reductive elimination to form a C-C bond is the rate-determining step.
“…Two early examples (Scheme 1 (c) and (d)) and two later examples (Scheme 1 (e) and (f)) are shown. The catalytic linear dimerization of acrylonitrile reported in the late 1960’s 8 , 9 ) has been later proposed by us 10 ) to involve the oxidative addition of a C–H bond β to the CN group onto the ruthenium, to give an intermediate such as 2 (Scheme 1 (c)).…”
The direct addition of ortho C–H bonds in various aromatic compounds such as ketones, esters, imines, imidates, nitriles, and aldehydes to olefins and acetylenes can be achieved with the aid of transition metal catalysts. The ruthenium catalyzed reaction is usually highly efficient and useful as a general synthetic method. The coordination to the metal center by a heteroatom in a directing group such as carbonyl and imino groups in aromatic compounds is the key step in this process. Mechanistically, the reductive elimination to form a C–C bond is the rate-determining step, while the C–H bond cleavage step is not.
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