Reactions of laser-ablated zirconium atoms within a supersonic expansion: insertion versus radical mechanism.
In a laser ablation type microreactor followed by supersonic expansion, zirconium atoms have been reacted with methyl fluoride, CH(3)F (MeF), and mixtures of MeF and dimethylether, CH(3)-O-CH(3) (DME) seeded in He. With both mixtures, only a number of simple fluorinated products are formed, and they have been identified by one-photon ionization. All products can be linked to radical reactions either with F atoms, CH(3), or ZrF(1, 2, 3) radicals. No insertion products of the Grignard reagent type, F -Zr-CH(3) could be identified with or in the absence of DME. On the other hand, evidence has been found for the presence of organometallic compounds of the type ZrC(2)H(n=2, 4, 6), which could result from radical attack. Thus, even in conditions where intense solvation is at work, induced by clustering with polar DME molecules, which can act as stabilizing agents, a direct insertion mechanism into the C-F bond involving barrier suppression is not at work in our conditions. The reactivity due to radicals is very effective in this type of reactor, and the products that are efficiently formed can be quickly stabilized in the expansion. The radical attack supersedes, in the case of zirconium solvated by DME, the metastable mechanism with Zr(4d)(3)(5s)(1), that is certainly energetically impossible in the absence of strong reaction barrier suppression by a solvent. High level ab initio calculations performed at the CASPT2 level of theory are used for characterizing the electronic and geometric structure of the inserted products. They also reveal striking features of the reaction mechanism that support the absence of observation of inserted products within solvated clusters of zirconium.
Soorkia
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Laboratoire Francis Perrin (CNRS-URA-2453) CEA/IRAMIS/Service des Photons, Atomes et Molécules, CEN Saclay, F-91191 Gif-sur-Yvette cedex, France.
Pothier
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Mestdagh
J M
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Soep
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Liévin
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