Issue 42, 2022

The activated reaction of dichlorocarbene with triplet molecular oxygen

Abstract

The well-known dichlorocarbene (CCl2, 1) is deemed to undergo an extremely facile addition reaction with triplet molecular oxygen (3O2) under formation of the corresponding singlet Criegee intermediate, phosgene O-oxide. This is unexpected, because the carbene possesses a singlet ground state with a large singlet–triplet gap and, typically, only triplet carbenes react swiftly with triplet dioxygen. Hence, we deployed a careful theoretical study of this reaction and computed the oxygen addition barrier at levels of electron correlation as high as CCSD(T) and BD(TQ) and basis sets as large as cc-pV5Z. Our results firmly establish the existence of a reaction barrier, and we estimate its height to amount to 8.8 kcal mol−1. Furthermore, the initially formed triplet dioxygen adduct is prone to facile O–O bond breaking rendering phosgene and triplet oxygen atoms likely products of the overall reaction. As a general conclusion, we find that carbenes are ambiphiles in oxygen additions and more electrophilic as well as that more nucleophilic carbenes show greater reactivity.

Graphical abstract: The activated reaction of dichlorocarbene with triplet molecular oxygen

Supplementary files

Article information

Article type
Paper
Submitted
23 авг 2022
Accepted
12 окт 2022
First published
20 окт 2022

Phys. Chem. Chem. Phys., 2022,24, 25834-25841

The activated reaction of dichlorocarbene with triplet molecular oxygen

J. P. Wagner, Phys. Chem. Chem. Phys., 2022, 24, 25834 DOI: 10.1039/D2CP03889G

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