Density functional theory investigation of the reactions of CH2Br–I, CH2I–Br, CH2Cl–I, and CH2I–Cl isopolyhalomethanes with ethylene

Literature Information

Publication Date 2002-09-16
DOI 10.1039/B204898C
Impact Factor 3.676
Authors

Dongqi Wang, David Lee Phillips, Wei-Hai Fang


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Abstract

We report density functional theory calculations that examine the chemical reactivity of the iso-CH2X–I and iso-CH2I–X (where X = Br or Cl) species with ethylene and their isomerization reactions. The carbenoid properties and isomerization reactions of these CH2X–Y species were compared to those found previously for the CH2X–X species (where X = I, Br or Cl). The chemical reactivity of the iso-CH2X–I and iso-CH2I–X species varies with the electronegativity of the X atom and the position of the X atom in the carbon–halogen–halogen moiety. In addition, the C–X–I or C–I–X bond angles and I–X bond lengths (which vary more than in the iso-CH2X–X species) also appear to influence the chemical reactivity of the iso-CH2X–I and iso-CH2I–X species. We briefly discuss the properties of these cyclopropanation and isomerization reactions and likely consequences for using different isopolyhalomethanes and other species as methylene transfer agents.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

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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