Gauging stability and reactivity of carbonyl O-oxide Criegee intermediates

文献信息

发布日期 2019-09-13
DOI 10.1039/C9CP03790J
影响因子 3.676
作者

J. Philipp Wagner


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摘要

In this study, we evaluated the effect of substitution on the stability and reactivity of carbonyl O-oxide Criegee intermediates (CIs). In this regard, we computed a set of more than 50 carbonyl oxides at the CBS-QB3 level of theory and assessed their stability by means of an isodesmic reaction equation defining a carbonyl oxide stabilization energy (COSE). Almost all substituents are stabilizing and amino groups in particular leading to COSE values of almost 60 kcal mol−1. As opposed to π-donors, substituents with a strong σ-electron pull destabilize the CO–O group. Furthermore, we studied how the intrinsic stabilization of the Criegee intermediate is reflected in its CO and O–O bond lengths as well as the partial charges on the individual atoms of the carbonyl oxide moiety. As a potential measure for reactivity, we determined the adiabatic singlet–triplet energy gap of all carbonyl oxides. Amino substituted CIs exhibit high-lying triplet states and have relatively large barriers towards addition of water or the OH radical. However, the ΔES–T cannot serve as a rigorous measure for carbonyl oxide reactivity.

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来源期刊

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 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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