Successive reactions of iron carbonyl cations with dimethyl ether: direct cleavage versus rearrangement

Literature Information

Publication Date 2002-04-12
DOI 10.1039/B108261B
Impact Factor 3.676
Authors

Sophie Le Caër, Michel Heninger, Pascal Pernot, Hélène Mestdagh


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Abstract

The reaction kinetics of electron impact ionization generated Fe(CO)n+ cations with dimethyl ether (DME) is investigated using a triple-cell Fourier Transform Ion Cyclotron Resonance spectrometer. The primary reaction is rapid substitution of CO by DME. One-step substitution of two CO ligands by one DME molecule also occurs for n = 3–4, and for unrelaxed Fe(CO)2+ ions. Successive substitutions in the Fe(CO)4+/DME system lead mainly to Fe(CO)(DME)2+, in which the last CO remains unsubstituted. This ion is slowly converted to Fe(CO)(DME)3+ and Fe(DME)2+. The latter reaction implies formation of neutral CH3COOCH3 resulting from iron-promoted CO insertion reaction. Further reaction of Fe(DME)+ with DME involves the cleavage of a C–O bond according to two channels, either direct CH3˙ loss or more exothermic CH4 loss, implying a molecular rearrangement. The branching ratio is strongly energy-dependent: the latter channel is observed only for Fe(DME)+ ions having a very low energy content.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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